The home side currently sit top of the table, but a draw away at Willem II before Christmas allowed PSV, who beat VVV-Venlo, to move one point behind them.
Ajax had to settle for a point in their last league match as they shared the spoils with Willem II, securing their first draw of the season.
Brazilian forward Antony gave the Amsterdam outfit an early lead just four minutes in but despite dominating the match with 74% possession, Ajax allowed the home side back into the game when Kwasi Okyere Wriedt's left-footed strike on the edge of the box swept past goalkeeper Andre Onana 10 minutes into the second half.
The 34-time Eredivisie champions remain at the summit despite dropping two points but are aware that a defeat this weekend would see PSV leapfrog them into first place.
Ajax boss Erik ten Hag has been pleased with his side's 2020-21 campaign, especially with their attacking prowess, which has seen them score an impressive 52 goals in just 14 top-flight matches – the most by any side in the Eredivisie. Ten Hag's men have also impressed defensively, conceding only 10 goals, the fewest in the top tier.
De Godenzonen, who are unbeaten in their last five home matches against PSV, would move four points clear of their opponents with a victory on Sunday.
PSV secured back-to-back 4-1 league victories against RKC Waalwijk and VVV-Venlo before Christmas, which extended their winning streak in all competitions to five matches.
Despite falling behind to Venlo in the 22nd minute, PSV controlled the game, with Philipp Max's penalty followed by strikes from Olivier Boscagli, Cody Gakpo and Adrian Fein, securing a comfortable victory.
PSV have been faultless on home soil this season, winning all seven of their matches played at the Philips Stadion, but they have only won three of their opening seven league games on their travels.
Manager Roger Schmidt will be aware of the threat posed by their opponents this weekend, who they have beaten only twice in their last 13 visits with their most recent success being a 2-1 win in October 2015.
De Boeren will head into Sunday's clash as the underdogs, but a victory would see them climb to the top of the table for the first time since mid-October.
Ajax Eredivisie form: WWLWWD
Ajax form (all competitions): LLWWWD
PSV Eindhoven Eredivisie form: DWDWWW
PSV Eindhoven form (all competitions): DWWWWW
Ajax full-back Noussair Mazraoui remains a doubt for this weekend's match but is likely to start if he is declared fit to play.
The visitors will be without Donyell Malen (knee), Armando Obispo (knock) and Erick Gutierrez (knee), while Eran Zahavi, who has not featured since the 1-0 win against Granada in early December, remains doubtful with an injury, as do New Zealander Ryan Thomas and forward Maximiliano Romero.
Teenage attacker Noni Madueke, who was born in Barnet, is expected to start up front alongside 21-year-old Cody Gakpo.
Ajax possible starting lineup:
Onana; Mazraoui, Schuurs, Blind, Tagliafico; Klaassen, Labyad, Gravenberch; Antony, Huntelaar, Tadic
PSV Eindhoven possible starting lineup:
Mvogo; Dumfries, Teze, Boscagli, Max; Sangare, Hendrix; Gotze, Ihattaren; Gakpo, Madueke
We say: Ajax 2-1 PSV Eindhoven
Both sides are striving for the Eredivisie title this season and will be intent on making a statement this weekend. PSV have key attacking players out injured and as a result will likely need something special from the likes of Gotze, Gakpo and Madueke to win this game. Ajax, who have a good record against their opponents, should just edge what is expected to be a tight encounter.