PSV come from behind to sink NEC
John Goossens put Nijmegen ahead eight minutes before the interval with a fierce 30-metre free-kick but directly after the break substitute striker Danny Koevermans struck from close range to level.
Ibrahim Afellay put PSV ahead midway through the second half following a fine solo run before Ola Toivonen scored his sixth in five matches to secure the points.
PSV are top with 13 points after five matches, ahead of Ajax Amsterdam who are also on 13 but have scored one goalless.
Ajax warmed up for their Champions League meeting at Real Madrid on Wednesday by defeating Willem II Tilburg 2-0 thanks to two Luis Suarez penalties.
Champions Twente Enschede stayed in touch with the leaders on 11 points after beating VVV Venlo 2-1 with Bryan Ruiz and Roberto Rosales on target.