There is one crumb of comfort for the Tottenham manager, as Dele Alli is expected to be fit to feature against the Eredivisie outfit, despite missing the win at Molineux over the weekend.
Spanish side Barca top the group on nine points, three ahead of second-placed Inter Milan of Italy.
Striker Kane finally levelled the contest when he fired home after being teed up by substitute Fernando Llorente.
Kane was to the fore once again in the dying embers of the contest, his headed attempted clipping Sainsbury on its way into the net to leave PSV on the brink of elimination.
Kane rose highest to win a header in a packed penalty area, with the ball hitting a teammate, then Sainsbury's leg - leaving Jeroen Zoet haplessly stranded in the PSV goal.
The stay-aways appeared to have made the right choice when PSV took their shock lead. Luuk de Jong with the header!
Spurs were leading 3-0 in the 61st minute at Molineux on Saturday but conceded twice from penalties, with both of the fouls coming from centre-back Juan Foyth on his Premier League debut.
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The hosts dusted themselves down and the chances soon racked up for them to have turned the game around by the half-hour mark.
'One game at a time.
"A bit bittersweet. My first game in the Champions League, a double deflection and it goes in off me for the victor", Sainsbury told Optus Sport's Mark Schwarzer. Donyell Malen nearly curtailed the Tottenham celebrations, but his rocket from the edge of the area was pushed away by Paulo Gazzaniga.
As for PSV, they will be relishing the opportunity to leap above their Group B rivals and stake their claim for Europa League football.
"It's s***", Van Bommel said of the pitch. The Dutch champions have grown into the tournament, and have genuine aspirations of upsetting the odds at Wembley on Tuesday evening. PSV's only point comes courtesy of the draw with Spurs in the Netherlands on 24 October.
In team news, winger Steven Bergwijn should be fit and is likely to be handed a starting place after missing out two weeks ago.
With only one point from the opening three games, PSV headed to London looking for an unlikely victory to get their Champions League campaign kickstarted.