Munro was born as eldest son of William Munro in Druid Stoke, Gloucestershire (now in Bristol) in 1818. In 1834 he entered the 39th (Dorsetshire) Regiment of Foot as an ensign. He was promoted Lieutenant in April 1836, Captain in July 1844, Mayor in May 1852 and Lieutenant Colonel in November 1853. He served many years with his regiment in India but during the Battle of Maharajpore he was severely wounded on 24 December 1843. In 1878 he achieved the rank of a General.
Munro became a Fellow of the Linnean Society of London in 1840. He conducted collecting expeditions to India (1834-1838), Kashmir (1847), and Barbados (1870-1875). His main research field were tropical grasses, including the bamboo species of which he published a monograph in 1868. The genera Munroa, Munronia and Munrochloa are named in his honour.
Discovery of Fossil Plants at Kamptee, 'Proc. Agr. Soc. India,' 1842, pp. 22-23
On Antidotes to Snake-bites, 'J. Agr. Soc. India,' 1848, vi. 1-23
Report on Timber Trees of Bengal, 'Edinburgh New Phil. J.,' 1849, xlvi. 84-94
Froriep Notizen, 1849, x. 81-7, 'Characters of some New Grasses collected at Hong Kong & in the vicinity by Mr. Charles Wright in the North Pacific Exploring Expedition,' 'American Academy Proceedings,' 1857-60, vi. 362-8
An Identification of the Grasses of Linnæus's Herbarium, now in possession of the Linnean Society of London, 'Linn. Soc. J.,' 1862. vi. 33-55
A monograph of the Bambusaceae. In: Trans. Linn. Soc. London. 26, 1868.