Emma Hayes's side hosted their London rivals at Stamford Bridge, where new signing Mia Fishel broke the deadlock on her debut for the club following her summer arrival from Tigres.
England protege Lauren James then doubled the Blues' lead with 51 minutes on the clock, before Martha Thomas gave Tottenham a slice of hope with a consolation goal 14 minutes from the end.
However, Chelsea shut up shop towards the end to cement their position at the top of the table alongside next weekend's opponents Manchester City Women, who saw off West Ham United Women 2-0.
Gareth Taylor's side could not find a way through in the first half, but quickfire strikes from Lauren Hemp and Jill Roord did the damage, and City also survived a 71st-minute red card to Leila Ouahabi.
The Citizens' arch-rivals Manchester United also made a winning start to the new WSL season, overcoming Aston Villa Women 2-1, despite falling a goal behind to the hosts through Rachel Daly's effort.
Daly drew first blood only two minutes after Villa's Kirsty Hanson was sent off, but Lucia Garcia extinguished the hosts' lead in the 79th minute, before Rachel Williams won it for Marc Skinner's team in the second minute of added time.
Arsenal Women's showdown with Liverpool Women drew a record-breaking 54,115-strong crowd at the Emirates Stadium, but the Gunners were left deflated as the Merseyside outfit came away with a hard-fought 1-0 win.
Clinching their first away victory in the WSL since January 2020, Liverpool struck through Miri Taylor three minutes into the second half and comfortably dealt with a plethora of ineffective Arsenal crosses.
Liverpool fans had another reason to celebrate on Sunday, as local rivals Everton Ladies fell to a 2-1 loss to Brighton & Hove Albion Women, as Elisabeth Terland struck a 14-minute brace before Megan Finnigan pulled one back.
Finally, the highest-scoring game of the day saw Leicester Women sink Bristol City Women 4-2, as Aimee Palmer, Shannan O'Brien, Lena Petermann and Jutta Rantala all got in on the act.
WSL WEEK ONE RESULTS IN FULL:
Arsenal 0-1 Liverpool
Aston Villa 1-2 Man United
Bristol City 2-4 Leicester
Chelsea 2-1 Tottenham
Everton 1-2 Brighton
West Ham 0-2 Man City