Tottenham took another big step towards qualifying for the last 32 of the Europa League as they won 2-0 away to FC Sheriff to make it three victories in a row in Group K.
The 31-year-old, now in his second spell with the north Londoners, rifled home his sixth of this year's Europa League to help Spurs secure a 2-0 victory. Not only did it leave the Spurs on the cusp of the knockout stages, but the strike saw Defoe equal Chivers' long-standing European scoring record.
The former England striker was part of the UEFA Cup-winning side of 1972 - a feat the current Spurs side look capable of matching. Favorites with the bookmakers, Tottenham are one of five teams in this year's competition to have previously lifted the trophy and have won all five matches this season without conceding a goal.
Their latest victory leaves them on the brink of Group K qualification, although the win at Sheriff was by no means easy. Previous matches in Tbilisi and Moscow were relative cakewalks in comparison to the 2,742-mile round trip to the communist state of Transnistria.
Despite having its own currency, police, army and border guards, the region remains unrecognised by any sovereign nations and, to all intents and purposes, is considered part of Moldova, whose league Sheriff have won 11 times since 2000. They impressed at a packed-out Stadionul Sheriff, although Jan Vertonghen headed the north Londoners ahead after just 12 minutes.
Vlad Chiriches was forced to make a stunning block at full stretch to prevent Henrique grabbing an immediate leveller, while Cadu, Ismail Isa and Richardinho also came close for the hosts. However, having seen Aaron Lennon, making his first start since the opening day, strike the post moments earlier, Defoe fired home with 15 minutes remaining to secure victory and his place in the record books.
Sheriff impressed early on, pressing quickly and causing the Spurs backline problems from the outset. The hosts managed three corners by the time Lennon saw a cross blocked by Djibril Paye for Tottenham's first in the 12th minute.
It was a set piece that proved costly to the hosts. Erik Lamela played it short to Christian Eriksen, whose cross was nodded into the top left-hand corner with impressive control by Vertonghen. Silence fell upon Stadionul Sheriff after the ball rippled the back of the net, although the raucous home support, complete with loud hooters, soon found their voice again.
Henrique, the top scorer in the Molodovan league, broke free on goal and looked all but certain to score after rounding Hugo Lloris, only for Chiriches to remarkably clear off the line. Kobi Moyal curled wide from outside the box as Sheriff continued to press, although that left them open to quick Spurs breaks.
Villas-Boas' side looked set to capitalise on that weakness when an Eriksen flick put Lennon through on goal, only for Vjekoslav Tomic to save the close-range drive with his legs. A lack of match sharpness was perhaps to blame for the miss, which looked like it would prove costly when Cadu found the back of the net on the half-hour mark.
An impressive cutback from Henrique put through his fellow Brazilian to rifle home past Lloris, only for offside flag to see the goal chalked off - not that the home fans noticed, celebrating for a full 30 seconds afterwards. The Moldovan champions were soon on the attack again, this time Isa breaking through and putting wide from an acute angle.
Not only were Tottenham having to deal with a clearly pumped-up home side but also a defensive re-jig, with Michael Dawson coming on for injured left-back Zeki Fryers after 34 minutes. Perhaps that alteration was behind their sloppiness when dealing with a quickly-taken free-kick, which ended with the impressive Henrique swivelling on the edge of the box and striking just over.
Defoe also fired over as the half came to a close, with the England international firing straight at Tomic seven minutes after the restart. Sheriff, though, were continuing to prove a threat, despite Tottenham dominating possession. Lloris had to react quickly to prevent a clear run on goal for Isa, who later looked for a penalty, writhing around in pain after a strong challenge by Sandro.
The Brazilian saw a long-ranger deflected behind at the other end and a threatening Eriksen cross was well dealt with by Tomic as Spurs looked to pull further ahead. Lennon's switch to the right flank was causing the hosts problems and the returning winger saw a 20-yard effort strike the post in the 67th minute.
Dawson got in the way of a Ricardinho drive when Sheriff pushed again, before Defoe put the tie to bed. Collecting a ball from substitute Nacer Chadli, the England striker rifled home to level with Chivers. Defoe wasted a chance to break the record soon after with what proved to be his last real chance, with Isa prodding wide late on for the hosts.