Liam Boyce fired his 10th goal in just 13 games this season as Hearts grasped their chance to claim the Premiership lead for 24 hours at least.
Robbie Neilson’s unbeaten Jambos leapfrogged Rangers and Hibs - who clash at Ibrox tomorrow - as they maintained their impressive run of form since stepping up from the Championship.
Boyce tucked home an early penalty after being brought down by Well keeper Liam Kelly.
He should have had another after Stephen Kingsley’s free-kick gave the Tynecastle men a two-goal half-time lead but saw Kelly make amends as he pushed away Hearts ' second spot-kick 10 minutes after the interval.
The Gorgie men had to stand firm in the closing stages as Graham Alexander’s men threw everything they had at the hosts.
But Neilson will be delighted with the grit his team showed to register their fourth clean sheet in the last five games.
Motherwell could also have moved top of the table had they managed a victory but instead remain fourth after failing to grab the capital gains they needed.
Hearts stuck to the same starting line-up that strolled past Livingston last week while Bevis Mugabi’s return for Ricki Lamie was the only change to the Well team that edged out Ross County.
Both teams started the day dreaming of climbing to the table summit but it took just three minutes for Well’s hopes to fade.
Liam Kelly was far too slow to react as Barrie McKay rolled a clever reverse ball in for Kelly.
The Northern Irishman got there first and went down as Kelly clipped his heels.
The goalkeeper desperately pleaded his innocence as referee David Munro pointed to the spot but there was certainly enough contact to merit the award.
Boyce tucked away the spot-kick as he maintained his blistering start to the campaign.
And Hearts were firmly in control by the 21 minute as Juhani Ojala’s foul on Beni Baningime handed the hosts a free-kick just outside the box. Kelly looked unsure who was taking the strike on as Kingsley and Ben Woodburn stood over the ball.
By the time he realised former Falkirk and Swansea full-back Kingsley was the man in charge the ball had already flown past him as he was beaten by a stunning set-piece.
Motherwell came close with a deflected Kaiyne Woolery effort and a dipping Tony Watt effort Craig Gordon had to tip over just before half-time.
Hearts should have gone three ahead 10 minutes into the second half but Kelly redeemed himself by saving another Boyce penalty after Munro dished out another debatable spot-kick award for a Callum Slattery barge on Cammy Devlin.
It took a big save from Gordon to prevent the Steelemen grabbing a lifeline as he pawed away Woolery’s low strike after Kevin Van Even got away with a blatant handball in the build-up.
With top spot at stake, it was understandable that nerves would play as the Jambos watched the clock tick down.
The hosts found themselves pinned in as Motherwell chased a lifeline but there was no beating Gordon as Hearts raced to the front of the Premiership field.
3 talking points
Hearts up for title fight
Hearts’ stay at the top of the table may only last 24 hours but it’s looking increasingly likely that Robbie Neilson’s side are ready for the long haul.
The winner of tomorrow’s Rangers-Hibs clash at Ibrox could take over the lead but the Jambos are showing the kind of qualities that will be necessary if they are to make a proper go of challenging at the top.
With Craig Gordon as reliable as ever in goal, there is a solid look about the Jambos.
The energetic Cammy Devlin has been another impressive addition to the midfield alongside Beni Baningime, while Liam Boyce - now on 10 goals for the season already - will be licking his lips at the service being provided from the likes of Barrie McKay and Ben Woodburn.
The Gorgie men remain unbeaten eight games into their first season back in the top flight and if they can keep this form up they will have a bit part to play in the title race this term.
Brilliant Barrie
With the Jack Grealish hair-do, there have been some cruel social media trolls who have dubbed Barrie McKay a Poundshop version of the Premier League ace.
But the ex-Rangers ace is worth an awful lot more to this Hearts side with the way he’s currently performing.
On current form it’s hard to believe he struggled to make his mark down south over the last couple of seasons.
But Robbie Neilson has quickly managed to bring the best out of the 26-year-old after luring him back to Scotland.
He was the instigator of the move which brought Hearts’ first penalty just moments into the game and gave Motherwell left-black Nathan mcGinlet a torrid time with his movement and pace.
But it wasn’t just going forward he was an asset to the new league leaders, with his graft work going back the ways also vital in the closing stages as Graham Alexander’s team threatened a comeback.
Game of two halves for Well keeper Kelly
There was a boost for Liam Kelly this week when Steve Clarke gave the Fir Park No.1 the nod over Zander Clark for a place in his Scotland squad.
But the Hampden boss could have been forgiven for having second thoughts as the half-time whistle blew at Tynecastle.
Kelly failed to read the danger in time as Barrie McKay rolled the ball in for Liam Boyce just three minutes in and his hesitation proved costly as he brought the striker down.
Boyce tucked away the penalty as Kelly dived the wrong way.
And he hardly covered himself in glory as he was beaten keeper’s side by Stephen Kingsley’s free-kick soon after.
But fair-dos to the former Rangers, Livingston and QPR stopper, who must have given himself a half-time talking to.
He redeemed himself by saving another Boyce penalty and pulled off a fine finger-tip save to push away a Beni Baningime shot that looked destined for the top corner.
