The game is known as 'De Topper' and comes as the sides' third fixture of the Eredivisie - Ajax and PSV occupying first and second respectively having won their first two games.
Hosts Ajax, who are chasing a fifth consecutive league title, began their defence in impressive fashion by routing Vitesse 4-1 and cruising past AZ 3-1 last weekend, while PSV have been even more emphatic in dispatching Willem II 3-1 and NAC 6-1.
Holland winger Memphis Depay has been in particularly eye-catching form for Eindhoven. The 20-year-old, who is reportedly attracting interest from Tottenham, has already racked up four goals this term and is expected to pose PSV's primary attacking threat.
Ajax's form goalscorer is Denmark midfielder Lasse Schone, who has notched three, and if the opening two games are anything to go by there will be no shortage of goals in the Dutch capital.
Last season, Frank de Boer's side edged PSV 1-0 in the corresponding fixture but suffered a 4-0 defeat at the Philips Stadion.
You can watch Ajax v PSV live from 3.30pm, this Sunday on Sky Sports 5HD