On March 6, 2008, it was announced that the Orange would join College Hockey America. Syracuse was the fifth school to join the conference for women's hockey.
Paul Flanagan, who coached the St. Lawrence Skating Saints women's ice hockey program to five NCAA Frozen Four appearances was appointed as the first coach for the Orange women's ice hockey program. Flanagan had been the 2001 ECAC and American Hockey Coaches Association Coach of the Year. For the inaugural season, Flanagan was joined by Graham Thomas, who played for Mannheim Jung Adler in Germany, and Erin O'Brien, a two-time All-American at Plattsburgh State, an NCAA Division III school for women's ice hockey.
Some of the first players for the team were transfer players from other schools. Gabrielle Beaudry, transferred to the Orange from Boston College. Cheyenne Bojeski was a transfer from Mercyhurst, while Julie Rising came to the Orange from Bemidji State. Lucy Schoedel and Stefany Marty were both transfers from New Hampshire.
The Orange's inaugural season was in 2008-09, and the team played its first ever game on Wednesday, October 1, 2008 at Colgate. During the first game Lucy Schoedel recorded 34 saves and Megan Skelly scored the first goal in Syracuse women's ice hockey history nine seconds into the game. Despite holding a 2-0 lead in the game, the Orange lost to Colgate by a score of 3-4. The following two games were against the eventual NCAA champion Wisconsin Badgers on October 2 and 3. Despite losing both games, Lucy Schoedel made seventy five saves in two games. A week later, Syracuse played in its first ever College Hockey America conference game. The Orange took on the Robert Morris Colonials. Lucy Schoedel recorded her 100th career save (and totaling 130 stops in just four games) in a 1-0 losing effort. Team captain Stefanie Marty scored her first goal for Syracuse on October 17. It was a 4-2 loss at Quinnipiac. Of note, Cheyenne Bojeski also scored her first ever goal for Syracuse. The following day, co-captains Julie Rising and Stefanie Marty would both score as Syraucse won its first ever game by a 2-0 tally.
March 5, 2009 was the first postseason game in Orange history. In the quarterfinal round of the College Hockey America tournament, the Orange were ousted by the Niagara Purple Eagles by a score of 3-2. Freshman forward Kylie Klassen made history by scoring the first playoff goal in the program's history.  Assists went to Megan Skelly and Julie Rising.
After a slow start to the season, the Orange won their first game of the season on October, 2009 in a 3-1 win over the Providence Friars. The win would be the first of a four game win streak after starting the season winless in the first six games. The start of the 2009-10 season was highlighted by eight straight road games to start the season, after a home exhibition game against the University of Guelph. By December 2009, the team was ranked in the ranked tenth in the USA Today/USA Hockey Magazine poll. The ranking marked the first time the Orange was nationally ranked in the program's history.
On March 5, 2010, the Orange won the first playoff game in program history. Sophomore Lisa Mullan scored two goals, as the Orange defeated Niagara by a score of 5-3. In addition, freshman Isabel Menard added three points. The Orange advanced to the CHA Championship against rival Mercyhurst but fell 1-3.
On October 1, 2010, by tying Northeastern in the season opener, it marked the first time that the Orange started the season unbeaten. Stefanie Marty had two goals in the game. Northeastern featured her twin sister Julia Marty. It was the first time the sisters had ever played against each other in their NCAA careers. With a 4-2 defeat of New Hampshire on October 8, 2010, the Orange is off to its best start in program history (1-0-1). In the win, senior transfer Ashley Cockell scored her first career goal for the Orange. Freshman goaltender Kallie Billadeau made 26 saves as she played in her first game for the Orange.
The Orange continued their best start in program history with a 2-2-1 record. The Orange registered a 7-1 win against Connecticut on the 16th of October. Syracuse’s seven goals against Connecticut ties for second all-time in Orange history. Twelve different players registered points. Isabel Menard recorded the first hat trick in school history and added an assist. In addition, freshman Sadie St. Germain scored her first career goal and had two assists in the win. The Orange outshot the Huskies 38-19. In faceoffs, they had a 38-17 advantage over them. On November 30, Kallie Billadeau set a Syracuse record with 57 saves in a 4-1 loss against No. 1 Cornell. As of December 6, 2010, Isabel Menard now has nine multiple-point scoring games this season, a Syracuse program record.
The Orange played the McGill Martlets women's ice hockey team in Montreal, Quebec. McGill was ranked number one in Canada, but Syracuse provided a valiant effort. The Martlets outshot the Orange by a tiny margin of 30-28 and won the game by a score of 4-2. Julie Rising and Megan Skelly each had two points for the Orange.