Tampines, who pipped Home United to the title last season, were pitted against DPMM at Thursday's 2012 season launch at the Live Wire, Marina Bay Sands, which featured a fixture draw for the first time in the competition's history.
DPMM created quite an impression the last time they played in the S.League in 2009, winning the Singapore League Cup and challenging for the league title briefly before they were removed from the competition following a ban by FIFA.
However, that suspension has since been lifted, allowing the club to participate in this season's S.League, although they will not have an easy start against Rovers.
Speaking at the season launch, Football Association of Singapore (FAS) president Zainudin Nordin spoke of his excitement and the impending season, which starts on February 9.
"This fixture draw marks the start of the 2012 Great Eastern-YEO's S.League which promises lots of excitement, especially with the two new teams, Harimau Muda and Brunei DPMM FC, which we hope will entice the fans to come down to the stadiums," Zainduin said.
S.League CEO Lim Chin also expressed his belief that the new season would be one to remember.
"It is great to kick off the 2012 season with this inaugural fixture draw, and especially so with all the club chairmen present," Lim said.
"Their presence today [Thursday] affirms their clubs' conviction in making the upcoming season one of the most eagerly anticipated ever.
"On top of that, we have two new teams in the S.League this season, Harimau Muda and Brunei DPMM FC. These two teams will definitely inject a whole new level of excitement into the game and we sincerely hope that Singaporeans will come down and support our S.League just like that have done so for the LIONSXII [participating in the Malaysia Super League]."
Harimau Muda, the Malaysia U-22 national team, will take part in the next four seasons of the S.League after an agreement was reached between the FAS and the Football Association of Malaysia (FAM), which also sees Singapore outfit LIONSXII take part in the Malaysia Super League.
Due to the late withdrawal of Etoile FC, this season will only see 13 teams compete in the S.League, meaning each round will see one team receive a bye.
Last season's runners-up Home United open against Balestier Khalsa, while perennial contenders SAFFC travel to play Albirex Niigata.
2012 S.League Opening Round Fixtures
Courts Young Lions vs Woodlands Wellington
Albirex Niigata vs SAFFC
Home United vs Balestier Khalsa
Gombak United vs Harimau Muda
Tanjong Pagar United vs Hougang United
DPMM FC vs Tampines Rovers
Bye: Geylang United