The Dutch defender became the initial backline player to net two goals in a English top-flight game for Spurs since the Belgian defender in spring 2013.
At a glance
Micky Van de Ven nods into the net two times in first half
Everton's Jake O'Brien has goal disallowed after video check
Pape Matar Sarr nets final goal in dying moments
The defeat is Everton's initial at their new ground
Micky van de Ven scored on two occasions as Spurs extended their winning streak in away games in the top division and delivered Everton their first defeat at their new home.
Everton were undefeated in their last five matches at their new ground at Bramley-Moore Dock, having left Goodison Park behind after more than a century at the end of last season.
But Tottenham's leader the Dutchman struck on two occasions from corners in the first half to place their impressive record at risk, and they were failed to mount a comeback before Pape Matar Sarr - assisted by former Toffees attacker Richarlison - nodded in a final goal to put the game to bed.
The Everton defender thought he had levelled the scores five minutes after Van de Ven's first goal, directing a powerful header past the Spurs keeper from an set-piece.
The Portuguese striker, meanwhile, missed a handful of opportunities, while Vicario made a succession of fine stops to guarantee the London club went five matches on the road without defeat in the Premier League.
But the VAR intervened, instructing the match official to review the goal on the screen and the official ruled that Jack Grealish and Iliman Ndiaye were in an illegal position and had impeded with the Spurs keeper.
The win moves Thomas Frank's team up to third in the Premier League, five points off north London rivals and table-toppers the Gunners.
Everton remain 14th and sit six points clear of the relegation zone.
Following a drab midweek performance in the European competition against Monaco, where they mustered a mere attempts on target, Frank chose Randal Kolo Muani up front instead of ex-Everton forward the Brazilian.
The summer signing was unable to make much of an impact before being substituted for Richarlison after an hour on the field, but it emerged he proved unnecessary in the final outcome.
Defender the Dutchman transformed into an offensive threat to be reckoned with.
Tottenham's first goal came from a well-worked corner routine, with the midfielder heading the ball toward the six-yard box for an unmarked the defender to score.
And the captain - stepping up as skipper in Cristian Romero's unavailability - notched his next goal in added time as he rose above the England keeper to head home.
The Dutchman was equally impressive in defence, combining well with his defensive colleague as the pair handled excellently with the numerous deliveries thrown their way by the opposition.
The club's new home had been a happy hunting ground, but it appears the freshness may have faded somewhat and fans flocked to the gates after Sarr's final goal for Spurs.
The break in the team's unbeaten home run will not be a massive worry for the manager, but their striker situation are.
Beto and Thierno Barry - the Everton's two established centre-forwards - had scored only a single goal between them before the weekend's match.
And they were unable to add to that poor record on a damp and dreary evening on in Liverpool.
The striker's performance was summed up when he chose to overhead kick a clear chance from close range, even with having room and opportunity to reposition for a more conventional shot that would have tested the keeper.
The substitute, too, failed to influence the game after coming on for Beto in the second half.
It was not for a shortage of chance. Most of the home side's attacks came through the winger and the forward, who relentlessly delivered dangerous crosses into the Spurs penalty area.
The Toffees: The team head to the Stadium of Light in the top flight on early November at 8 PM.
Spurs: The London club go to St James' Park on late October for their next round Carabao Cup match against the Magpies.
Elara is a writer and life coach passionate about sharing stories of transformation and resilience.
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