The excellent form of the Belgian, who is the most popular player in the game with 52.2 per cent ownership, meant he was given the armband by over 857,000 FPL managers for Manchester City's trip to Southampton.
But De Bruyne's run of five attacking returns since the restart - three goals and two assists - was brought to an end as he was benched from the start and could do nothing after coming on in the second half to prevent a 1-0 defeat.
De Bruyne was the second-most popular captain behind Mohamed Salah (£12.6m), who was given the armband by 1.2million managers.
GW33+ most-captained players
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Salah was entrusted with the armband by 42 of the top 100 managers but they and the 1.2million were perhaps seeking more than the single assist that the Liverpool star returned in the 2-0 win at home to Aston Villa.
Manchester United players were also backed by the leading 100 FPL managers.
Martial scored a stunning goal and provided two Fantasy assists in the 5-2 victory against AFC Bournemouth on Saturday, while Fernandes claimed 15 points thanks a goal and two assists of his own.
GW33+captains by FPL's top 100
More than 1.1million managers signed one of Ole Gunnar Solskjaer's men ahead of the deadline and those transfers paid off in a 5-2 victory.
Man Utd occupied the top three spots among the most popular transfers for Gameweek 33+.
Fernandes was acquired by 253,000+ after averaging 8.1 points per match this season, more than any other player in Fantasy, while Mason Greenwood (£4.5m) was snapped up by 230,000+.
Neither disappointed, with Greenwood scoring twice at Old Trafford and getting a 13-point haul that was only beaten by Fernandes and Martial's 14.
GW33+ most transfers in
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But the 151,000 managers who transferred out Vardy were punished after the striker scored his 100th and 101st Premier League goals in the Foxes' 3-0 victory over Crystal Palace on Saturday.
GW33+ most transferred-out players
|Player||Transferred out by ('000s)|