Jess Carter headed the Blues in front after seven minutes, however they were pegged back when Bethany England scored against her former club.
James cut inside and fired in off the post to restore Chelsea’s advantage, before Guro Reiten secured the win.
It condemned Spurs to a sixth straight defeat in the league, despite Nikola Karczewska’s late strike.
Chelsea have now won all seven of their WSL matches against London rivals Spurs.
Emma Hayes’ side return to the WSL summit and lead Manchester United by two points after they were held at home by Everton.
Chelsea are unbeaten in 19 matches in all competitions, having not lost since a 3-2 defeat by Liverpool in their opening game of this season.
Chelsea march back to the summit
Having dropped points for only the second time in this WSL campaign last time out at Arsenal, Chelsea started well and deservedly took an early lead at Brisbane Road.
A well-worked move from a corner saw Erin Cuthbert cross in from the edge of the box and an unmarked Carter headed home the opener.
It was a case of deja vu for Spurs, who have been in rotten league form and had scored just twice while conceding 15 in six previous top-flight games against Chelsea.
Their losing run in the WSL is their worst in the competition and they had failed to score in their past three matches.
Carter’s goal was the fifth they have conceded in the opening 15 minutes of WSL games this season – more than any other side.
England scores but Spurs woes continue
To remedy their scoring woes, Spurs boss Rehanne Skinner signed England from Chelsea for a reported £250,000 – a record between two WSL clubs – and the Euro 2022 winner showed her value on 16 minutes.
The equaliser came against the run of play with Tottenham’s first move forward of note. Ashleigh Neville slid the ball to Drew Spence who beat her marker before slotting in England, who tapped home before declining to celebrate against her old team.
Signing England has given Spurs much more of an attacking threat. However, they remain vulnerable in defence, as James proved.
On 27 minutes, she ran unchallenged from the wing into the centre of the pitch and restored Chelsea’s lead with a fine individual goal from the edge of the box, which owed plenty to Spurs failing to put James under pressure
Chelsea were then able to keep Spurs at arms length before bagging a third on the hour, Sam Kerr flicking a long ball into the path of Reiten who slotted the ball into the bottom corner.
Karczewska gave Spurs hope with two minutes to play with a fine low finish, but Chelsea held on to move top.