Ajax will host AZ Alkmaar on Thursday, two days after PSV will travel to second-bottom NAC Breda, meaning Frank de Boer's men are likely to be 12 points behind their Eindhoven-based rivals at kick-off at Amsterdam Arena.
Winless in their past two matches, Ajax have dropped to nine points behind PSV, who have won seven straight games.
Speaking after Ajax's 1-0 loss at Vitesse Arnhem on Sunday, midfielder Davy Klaasen slammed his team's 'amateur' performance.
"I really thought today we played as amateurs. More I cannot do," Klaasen told Fox Sports.
"We have to win our games and then hope that PSV will collapse. That's what we should do. It should at least be better than today."
Ajax's poor form has come as rumours claiming De Boer may leave for Newcastle United gain momentum.
With Alan Pardew having left St James' Park for Crystal Palace, Newcastle are looking for a new manager and De Boer is considered a genuine option as Ajax have drawn with Feyenoord and lost to Vitesse.
But Ajax director of football Marc Overmars said his former club and international team-mate will stay in Amsterdam.
"I do not think he will leave after this season and I hope it does not happen," Overmars told Voetbal International.
"We are very happy with Frank and we want to continue with him for years."
AZ will arrive in Amsterdam in fifth position in the Eredivisie after a 3-1 defeat of Heracles on Sunday.
John van den Brom's men will be looking to become the first AZ side to win at the Amsterdam Arena in the league, but they will have to do so without Celso Ortiz, with the Paraguayan midfielder having broken his arm against Heracles.
On Tuesday, PSV will travel to NAC hoping to extend Breda's winless run to six games in the Dutch top division, just three days after their come-from-behind 2-1 victory over Willem II.
Memphis Depay struck the winner in the 87th minute to join Heerenveen's Marc Uth as the league's top scorers with 12 goals.
Third-placed Feyenoord will hope to take advantage of any Ajax slip-up by winning at Heerenveen on Wednesday, while PEC Zwolle - who are fourth - will look to the same against bottom club Dordrecht.
Go Ahead Eagles and Excelsior will start the mid-week round on Tuesday, while ADO Den Haag will host Twente, Utrecht will visit Willem II, Vitesse will clash with Cambuur and Heracles face Groningen.
