The four-time European champions were the overwhelming favourites to beat a side chasing their first major trophy in April's KNVB Beker final, but doubles apiece from teenage winger Ryan Thomas and Guyon Fernandez propelled PEC from an early deficit to a stunning 5-1 victory.
Ron Jans' side followed that up with a 1-0 win over Ajax at the Amsterdam Arena in the Johan Cruijff Schaal in August, and they head to the same stadium on Sunday with 21-year-old playmaker Jesper Drost and big Czech Republic striker Tomas Necid in fine form.
Ajax have won their last three Eredivisie matches, with Kolbeinn Sigthorsson bagging a hat-trick last time out in a 5-2 win at NAC Breda to leave the defending champions level on points with PSV and PEC.
PSV, top on goal difference but having lost two of their past three league games, will expect a comfortable victory against newly promoted Excelsior in Eindhoven.
Heerenveen have collected 13 points from a possible 15 in their last five games to leap to fourth, one point off the pace.
Kristoffer Nordfeldt, arguably the division's in-form goalkeeper this term, and German forward Mark Uth will now test themselves away at Willem II.
New AZ coach John van den Brom makes his home debut against Twente.
"I didn't come here to finish sixth," said the former Anderlecht coach.
"I came here to really achieve something. I urge my players to go and do it."
Van den Brom will be wary of Luc Castaignos, who has netted eight goals in his last six appearances for Twente in all competitions.
Feyenoord arrested a run of four straight losses in all competitions with an Elvis Manu-inspired 4-0 win at Go Ahead Eagles last time out.
Fred Rutten will now unleash the 21-year-old winger on Groningen.
Heracles, who have lost all seven of their Eredivisie matches, aim to kick-start their season at home to fellow strugglers NAC Breda.
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