Ron Jans' men stunned the Amsterdam outfit by staging a 5-1 demolition job to pick up their first piece of major silverware back in April, and were at it again in Dutch football's annual curtain-raiser.
Stef Nijland scored the game's only goal 10 minutes into the second period, sending the ball beyond Kenneth Vermeer from a Kamohelo Mokotjo cross.
Zwolle's cup triumph came at Feyenoord's De Kuip, but for the Shield they headed to the home of their opponents - the Amsterdam Arena.
Ajax were without a host of World Cup stars, including Jasper Cillessen, Daley Blind and Joel Veltman, but started brightly and could have been ahead early on when Nick Viergever hit the post.
The Eredivisie champions continued to dominate, but the first use of vanishing spray in the Netherlands was the biggest talking point for the remainder of the first half.
Despite their early dominance, Ajax found it difficult to repond after falling behind to Nijland's effort and almost found themselves two down when Jesper Drost went close.
And there were to be no more goals as Zwolle got their season off to a superb start, while Frank de Boer will have plenty to think about as Ajax go in search of a fifth consecutive Eredivisie crown.
