The Eindhoven giants now sit top of the table following three wins from three under new coach Philip Cocu as AZ and surprise package Zwolle both emerged victorious
PSV's excellent start to life under Phillip Cocu continued as they defeated Go Ahead Eagles 3-0 on Saturday ahead of their Champions League qualification clash with Milan in midweek.
The Philips Stadion outfit made it three from three for 2013-14 as they claimed top spot in the Eredivisie standings by virtue of goal difference.
Florian Jozefzoon opened the scoring just three minutes into the second half with a close-range finish, before two fine long-distance efforts from Oscar Hiljemark and Memphis Depay wrapped up the points.
PSV were joined in extending their 100 per cent record for the season later in the day, when Zwolle smashed rock-bottom NEC 5-1 away from home.
Fred Benson netted twice for the visitors, while the Nijmegen outfit completed the scoring courtesy of a consolation strike from Cristoph Heimlein in the 76th minute.
Groningen went into Saturday's fixtures also looking to earn their third win of the new campaign, but they came unstuck as they suffered a 4-1 defeat to top-flight new-boys Cambuur.
Michiel Hemmen, Erik Bakker, Ramon Leeuwin and Wout Droste shared out the goals for the hosts as Michael de Leeuw struck for Groningen.
Elsewhere, AZ followed up their excellent win over reigning champions Ajax by beating RKC Waalwijk 2-1 away from home.
Aron Johannsson opened the scoring in the fourth minute for AZ but it looked like they might have to settle for a point when Jean David Beauguel netted with seven minutes left.
However, Maarten Martens responded just 60 seconds later to help the visitors leapfrog their hosts in the standings.
Meanwhile, at the Parkstad Limburg Stadion, Roda JC and Vitesse shared a 1-1 draw courtesy of goals from Marc Hocher and Valeri Kazaishvili.