Linking up well with Gareth Bale and the impressive Tom Carroll, the striker showed poise and his famed predatory instinct to convert three smart finishes, which were sandwiched around a mix-up between Kyle Naughton and Hugo Lloris to give the visitors a momentary glimmer of hope.
Emmanuel Adebayor was handed his first start of the season after, as exclusively revealed by Goal.com on Thursday, holding a second round of talks with manager Andre Villas-Boas regarding his role at the club. The striker partnered Defoe up front, with Lloris, Michael Dawson, Naughton and youngster Carroll the four other changes from the weekend loss to Wigan. Zeljko Filipovic replaced Dejan Mezga in midfield in the only change from the Maribor side which drew 1-1 in Slovenia two weeks ago.
A tame opening to proceedings was intermittently brought to life through the pace and guile of Gareth Bale down the left flank. The winger found space behind right-back Martin Milec time and time again, first feeding Adebayor inside the area after a quite brilliant first touch and spin, before whipping another whipped cross that the Togo international and Defoe failed to control under pressure.
The home side did not have to wait long to break the deadlock and, unsurprisingly, it came from the foot of the Welshman. With Maribor continually on the back foot, Milec gave Bale all the time in the world to pick out a cross after deciding against closing him down, and the winger duly found the onrushing Defoe inside the area to side-foot past Jasmin Handanovic.
Spurs didn't let up after going in front, with Lennon and Walker on the right following Bale's example and the former skipped past a scattered Maribor defence to find the right-back, but Walker's header was tame.
With the game heading towards half-time, and the Slovenians barely having ventured out of their own half, one mistake from the dominant home team and Maribor were level.
Lloris calmly cleared the ball to Naughton, only for the makeshift left-back to return the favour and put the goalkeeper under pressure with Robert Beric able to divert it goalwards and pull his side level as the former Lyon man attempted to round the striker.
The second half started in a similar fashion to the first, and Spurs found themselves back in front after just four minutes when the impressive Carroll threaded a fine through-ball into the path of Defoe to convert clinically past Handanovic.
The home side should have doubled their advantage soon after when the dazzling Bale scooped a pass over a static Maribor defence to find Adebayor clear inside the area, only for the striker to send his half-volley the wrong side of the post from 12 yards.
And the game's two best players put the game beyond doubt with just over 10 minutes remaining when Bale was sent raring down the left wing by an inch-perfect through-ball by Tom Huddlestone to send a low drive into the path of Defoe to claim his hat-trick.