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Gopikabai was noticed by Radhabai, the mother of Peshwa Baji Rao I during her visit to the Raste family. Radhabai was impressed by Gopikabai's orthodox observance of religious fasting and rituals and selected her to marry Balaji Bajirao (later called Nanasaheb Peshwa), the second son of Baji Rao I. Gopikabai was well versed in priestly religious matters and the prevailing customs followed in priestly Brahmin families.
Orthodox upbringing 
Gopikabai faced severe drawbacks in her later life as she was underexposed or never given proper training in handling court administrative or military matters. Her orthodox religious upbringing was thought to be a major cause of her haughty behaviour and narrow-minded outlook. Some of the crueler decisions which Gopikabai took in later life, including severing relations with her husband and her second son Madhavrao are traced to her orthodox upbringing. Gopikabai’s religious upbringing left her unable to understand court politics which Shahu and Nanasaheb Peshwa were pursuing.
Envy and ego 
After her husband became Peshwa, Gopikabai was unable to get along with the other women in the Peshwa household and developed a rivalry with her cousin Anandibai who was married to the Peshwa's brother Raghunathrao. There was also a rift between Gopikabai and Parvatibai, the wife of the Peshwa's cousin Sadashivrao Bhau which occurred when Shahu and Nanasaheb Peshwa selected Parvatibai’s niece Radhikabai to marry her eldest son Vishwasrao. Gopikabai insisted on sending Vishwasrao along with Sadashivrao Bhau (Bhausaheb) to battle against Abdali as she did not want Bhausaheb to take all the accolades after defeating Abdali and wanted Vishwasrao to play a bigger role. She did this to ensure that Vishwasrao becomes the next Peshwa after Nanasaheb. She suspected Nanasaheb of planning to make Bhausaheb the next Peshwa.
Death of Nanasaheb Peshwa 
Gopikabai blamed Radhikabai for being a bad omen and causing the death of her son Vishwasrao during the Third battle of Panipat. Instead of giving emotional support, Gopikabai continually nagged Nanasaheb Peshwa that he was responsible for the death of her son which was a major cause of Nanasaheb Peshwa's death from depression at Parvati near Pune.
Ascendency and reign of Madhavrao 
After the death of Nanasaheb Peshwa, a dispute arose about appointments in the Peshwa administration. Chhatrapati Shahu had died without an heir and by this time the post of Peshwa had become hereditary. Gopikabai, advised by her brother, attempted to involve herself in administrative matters. Since Vishwasrao, Nanasaheb's first son and legal heir, had already died, a dispute arose whether Madhavrao, Nanasaheb's second son or Raghunathrao, Nanasaheb's younger brother should ascend the post. This was fueled by the fact that Gopikabai’s relations with Anandibai, the wife of Raghunathrao, were not cordial.
Finally, it was decided that Madhavrao would ascend the post of Peshwa, under the guidance of Raghunathrao. This decision was a setback for Gopikabai who had hoped to have a controlling influence over her son on becoming the Peshwa but now would have to take up matters with Raghunathrao, who in turn was under the strong influence of his wife Anandibai. Moreover, Gopikabai's lack of proper training for court administration made her susceptible to poor advice from courtiers spoiling her relationship with her son. With help from her brother Sardar Raste, who had become an influential moneylender, she tried to influence her son Madhavrao Peshwa.
Madhavrao Peshwa started taking an active part in administrative matters and displayed an intelligent decision-making ability. Gopikabai urged him to be assertive and do away with Raghunathrao's control over his administration. A few wrong decisions on Raghunathrao’s part caused a wide rift in the administration. Sardar Raste collaborated with Nizam of Hyderabad and Bhonsale of Nagpur during their invasion of Pune against Raghunathrao’s administration.
Confinement at Nashik 
By sidelining Raghunathrao, Madhavrao Peshwa assumed control of the Peshwa administration. One of his first acts was to punish those who had assisted Nizam, prominent among them Sardar Raste. Gopikabai, who pled for mercy for her brother, was sternly warned of the consequences of such an act and was told not to interfere in administrative matters. When she persisted, she was confined to Nashik. Gopikabai remained at Nashik, performing orthodox Hindu rituals, until the death of Madhavrao in 1773 from tuberculosis. As Madhavrao died without an heir, Raghunathrao again made his claim for control of the Peshwa administration at Anandibai's insistence.
Return to Pune 
Narayanrao, Gopikabai's third son, was appointed Peshwa. Upon Narayanrao's appointment, Gopikabai returned to Pune and again began to interfere in the administration. During this time, Gopikabai involved herself increasingly in religious rituals. This was during an era when the Brahmin way of life was at its zenith, and huge monetary grants were given for performing religious rituals. The priestly class occupied an important administrative post.
Narayanrao's administration was paralyzed by debt and increasing opposition to him especially from Raghunathrao and Anandibai led to him being murdered. This incident was another setback for Gopikabai, and she again lost the control which she had gained a year and a half earlier and had to return to Nashik.
Life as a pauper 
As per her orthodox upbringing Gopikabai vowed to live the rest of her life as a holy beggar. She carried a dry coconut shell as a begging bowl and would beg outside the wadas of the Sardars who had retired to the holy city of Nashik. She would not collect alms from servants, but would only collect offerings from mothers, wives or daughters of high-ranking Sardars.
Radhikabai, the former fiancée of Gopikabai's late first son Vishwasrao had come to Nashik on a pilgrimage during the Kumbh Mela and was staying with her father Sardar Gupte. Once, Gopikabai unknowingly begged for alms outside their residence where she met Radhikabai who had come out with an offering. Gopikabai accused her of being bad omen and the primary reason for Gopikabai's ill fate.
Gopikabai fasted the rest of the month she met Radhikabai and on 11 August 1778 succumbed to dehydration. Radhikabai performed her last rites and erected a deepmala (light tower) on the banks of the Godavari river in Nashik. During the floods of 1961 this deepmala was washed away, leaving only a foundation where people put an oil lamp while performing last rites for their kin.
- Patil, Vishwas. Sambhaji.