Not even the sending off of Douglas after 51 minutes could halt Twente's ability to find the goal.
Twente are second in the table, level on 48 points with PSV and one behind AZ Alkmaar but with a game in hand.
Ola John opened the scoring for Twente after eight minutes with a well-placed drive and Willem Janssen doubled the lead on the counter-attack.
Leroy Fer set up Peter Wisgerhof after 35 minutes for a third while a diving header from Luuk de Jong settled the match before the interval.
Ola Toivonen pulled one back for PSV four minutes after Douglas had been shown a straight red card but Fer added Twente's fifth.
Toivonen scored again for the home side eight minutes before time only for Janssen's second to complete PSV's humiliation.
Ajax Amsterdam climbed into fourth with 46 points after four second-half goals, three from Lorenzo Ebecilio, gave them a 4-1 win over Roda JC Kerkrade.
Sanharib Malki had put Roda ahead five minutes before the break.
Ebicilio equalised for Ajax midway through the second half and added two more in the final minutes. Vurnon Anita got the other for Ajax.
Sixth-placed Feyenoord closed to within four points of the leaders thanks to Jordy Clasie's long drive after an impressive run sealed a 1-0 home win over Groningen who had Johan Kapelhof sent off two minutes before time.
