Luiten's par four at the 18th hole, the first playoff hole, was enough to clinch victory after he and the experienced Jimenez had finished the fourth round on 12 under par.
The 49-year-old Jimenez, who began the day a shot behind Luiten, roared to the top of the leaderboard with three consecutive birdies from the second and reached the turn one ahead of Luiten.
Luiten picked up birdies at the 12th and 14th and there was nothing to separate the two players as they reached the par-three 17th where both found a greenside bunker off the tee.
Neither could save par but they achieved regulation fours down the 18th to force a playoff where a poor tee shot by Jimenez deprived him of his 13th victory since turning 40.
"I don't know what it means for Dutch golf but I think it's pretty big," Luiten said.
"Maarten Lafeber won it in 2003 and that was huge, and to have another Dutch winner now I think it will help the game here and hopefully we can create more Dutch winners for this tournament.
"I can't believe it yet, it's unbelievable. I think tonight it will hit me."
It was Luiten's second European Tour victory of the season, after he won in Austria in June, and takes his earnings this year to over one million euros.
Englishmen Simon Dyson and Ross Fisher, France's Gregory Havret and Ireland's Damien McGrane were tied for third spot, three shots adrift of the leaders.