Excelsior went ahead after six minutes against PSV through Daan Bovenberg but the home side were in front before the interval with Jeremain Lens and Wilfred Bouma scoring.
Ola Toivonen extended their lead early in the second half before Guyon Fernandez pulled a goal back for Excelsior. Brazilian Marcelo sealed PSV's win 12 minutes before time.
Matthew Amoah scored the winner for NAC in the last minute against Twente after team mate Ali Boussaboun had struck nine minutes from time to cancel out Bryan Ruiz's opener in the 21st.
Twente had gone ahead after a fine attack led by Nacer Chadli and Marc Janko before Boussaboun equalised with a shot from a tight angle.
The visitors were sunk when a defensive blunder by Thilo Leugers allowed Amoah to score for NAC.
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