Ajax, who were a point behind 2010 champions Twente going into the match, sealed victory thanks to two goals from Siem de Jong.
De Jong put Ajax ahead midway through the first half when he struck from a tight angle to convert Gregory van der Wiel's cross, while an own goal by Denny Landzaat doubled the lead two minutes into the second half.
Theo Janssen pulled one back a minute later and Twente poured forward in search of an equalizer that would have put them back on course for a successful title defense before De Jong broke through 12 minutes from time for the clinching third.
Victory made it a first league title for Frank de Boer, who began his coaching career by replacing Martin Jol in December last year.
"Today we deserved the win the way we played," De Boer told Eredivisie Live TV. "We had some tough phases in this match but we got through it and finished it well."
