Both sides rounded off their respective European group-stage campaigns in the week and know they will compete in the Europa League playoff round next year, but now attention turns to a domestic title race that looks set to be as close as ever.
Match preview
Despite a comfortable 3-1 victory at the home of Champions League whipping boys Rangers on Tuesday night, due to defeats to Napoli and Liverpool in the previous two matchdays, Ajax had to settle for third place in Group A and a spot in the knockout stages of the Europa League.
Alfred Schreuder would have loved to provide Champions League knockout football for his new side, not only as he craves his own success with Ajax, but also in an attempt to fill the boots of former boss Erik Ten Hag in what is a demanding managerial position at the biggest club in the Netherlands.
Ajax are looking to record a fourth consecutive Eredivisie title this year and have started as serious contenders for the Dutch throne would, dropping just five points in their opening 11 matches and averaging over three goals per game.
AZ Alkmaar handed Schreuder's side their only loss of the campaign so far in the middle of September, a result which was followed by a frustrating home draw with Go Ahead Eagles, but since then Ajax have won all three of their league matches, bagging an impressive 15 goals in the process.
With struggling sides Vitesse and FC Emmen the final two opponents after a clash with PSV before the World Cup break, Ajax will be very aware of how significant this next week could be in securing a Dutch league title that has become more of an expectation than a hope for supporters in recent times.
PSV booked a spot in the knockout stages of the Europa League on Thursday night with a 2-1 victory in Norway against a dangerous Bodo/Glimt side, with only Arsenal's narrow win over FC Zurich at the same time preventing the Dutch team from topping a competitive group in UEFA's secondary club competition.
Ruud van Nistelrooy's exciting set of players have made serious waves in the Netherlands as well as on the continent so far this season, and currently sit only a point off their hosts on Sunday, having collected 27 points from their opening 12 domestic matches.
A deadly double-act at the heart of PSV's attacking prowess so far has been the partnership between youngsters Cody Gakpo and Xavi Simons, who top the goalscoring charts in the Eredivisie with nine and eight strikes respectively.
Nineteen-year-old Simons was under the media spotlight from a very young age during his time with the Paris Saint-Germain academy and senior side, but now being provided with regular gametime, the Netherlands international is thriving and beginning to fulfil his undoubted potential on the biggest of footballing stages.
A repeat of PSV's last visit to Ajax would suit them nicely this weekend, with Schreuder's side running out 5-3 winners in a thrilling Dutch Super Cup final back in July, a game which included a stunning hat-trick from Guus Til.
Ajax Eredivisie form:
W
L
D
W
W
W
Ajax form (all competitions):
W
L
W
W
L
W
PSV Eindhoven Eredivisie form:
W
L
W
W
L
W
PSV Eindhoven form (all competitions):
W
L
L
W
W
W
Team News
Ajax boss Schreuder has a few injury concerns ahead of Sunday's huge match, with Owen Wijndal and Steven Berghuis not taking part in team training on Friday due to their respective knocks picked up in the win at Ibrox on Tuesday.
Both players are expected to train on Saturday but it will be a close call on whether either can feature against PSV the next day, with the availability of Berghuis more likely than Wijndal's.
Brian Brobbey completed full training on Friday and is set to lead the line for Ajax as he looks to add to his team-leading eight Eredivisie goals so far this campaign.
PSV's medical room is still brimming with activity and Van Nistelrooy will be unable to call on the services of Kjell Peersman, Olivier Boscagli, Marco van Ginkel, Ismael Saibari and Yorbe Vertessen due to their respective injuries.
English defender Jarrad Branthwaite is expected to still be out with illness on Sunday, with the ex-Everton youngster only managing three league starts so far this season.
Ajax possible starting lineup:
Pasveer; Sanchez, Blind, Timber, Bassey; Klaassen, Alvarez, Taylor; Berghuis, Brobbey, Tadic
PSV Eindhoven possible starting lineup:
Benitez; Teze, Ramalho, Obispo, Mwene; Gutierrez, Veerman, El-Ghazi, Simons, Gakpo; De Jong
We say: Ajax 3-2 PSV Eindhoven
Sunday sees a clash between the Eredivisie's title contenders and most prolific attacks in what promises to be an exciting watch for neutrals and supporters alike.