Luiten became the first Dutch winner of his country's national open since Maarten Lafeber in 2003 and the first Dutchman to win twice in a season on the European Tour. He also won the Lyoness Open in Austria in June.
Jimenez made four early birdies to take the lead but Luiten rallied on the back nine at the Kennemer Golf & Country Club, with both making par on the 18th to force the playoff. Jiminez shot a 3-under 67 while Luiten had a 68. Both finished with 12-under totals of 268.
''It was tough. He was playing really, really good, especially on the front nine,'' Luiten said of the far more experienced Jimenez. ''I thought 'I just have to hang in there until the back nine and hopefully I can make a move there,' and luckily it happened.''
The players returned to the 18th tee and Luiten made par, while Jimenez hit his drive into the rough right of the fairway, left his second on the fringe and could not hole out in two.
On the back nine, Jimenez missed a birdie putt on the short par-5 12th, while Luiten sank his birdie putt to draw even at 13 under.
But the Spanish veteran, who won this tournament 19 years ago, responded immediately by rolling in a birdie on the 13th and stretched his lead to two strokes as Luiten's par putt slid past the hole.
Luiten birdied the 14th and Jimenez bogeyed the 15th and 17th to drop back level with Luiten and set up the playoff.
Three-time champion Simon Dyson's challenge for a fourth Dutch title faded at the 15th when he made a double bogey on the tough par 3. He finished tied for third at 9 under with Gregory Havret of France, Ross Fisher of England and Irishman Damien McGrane.