Muntz, whose best finish here is a tie for eighth, is one shot clear of Soren Hansen and John Bickerton. Hansen tied for second here in 2003 and Bickerton tied for seventh back in 2005.
Hansen is battling for a spot on the European Ryder Cup team. He holds the 10th spot on the team, but is just ahead of Martin Kaymer.
'I actually started thinking about it around the British Open Championship, but then I wasn't playing great and it's not good to think about that when you are not playing well,' Hansen said of the Ryder Cup. 'I really want to make the team, especially after how the last year and a half has gone. This is what we play for.'
Alexander Noren is alone in fourth at 4 under, while eight players, including Justin Rose, are tied at 3-under-par 67.
'I'm really pleased,' said Rose, who is eighth on the Ryder Cup points list. 'I knew coming here that there would be a lot of attention on the Ryder Cup, but I just had to try to get into the mindset of playing tournament golf.'
Muntz, the 2000 Qatar Masters winner, opened with a birdie on the par-5 second. He parred the next three holes before sinking his second birdie on No. 6 at Kennemer Golf & Country Club.
The 39-year-old from Holland ran off three consecutive birdies from the 10th to jump to 5 under. Muntz drained an eight-foot birdie putt at the 16th to secure the first-round lead.
'It's awesome playing in front of your home crowd and it was a gorgeous round, the kind you plan on paper and it actually works out,' Muntz stated.
Hansen dropped in back-to-back birdies from the second and moved to 3 under when his birdie try at the par-3 eighth found the bottom of the cup.
However, the Dane stumbled to a double-bogey on the par-4 ninth. He rebounded with four birdies on the inward nine to share second place.
'I made a double-bogey on the ninth, which is one of the toughest holes we play all year,' Hansen explained. 'But I followed that with birdies on 10 and 12 and that was the key to getting it back quickly and allowed me to try and shoot a really good score. I played well today.'
Bickerton posted a bogey-free 65 with three birdies on the front nine and two more around the turn.
Rose was joined in a share of fifth place by Phillip Price, Raphael Jacquelin, Anthony Wall, Simon Khan, Damien McGrane, Rafael Echenique and Jean-Baptiste Gonnet.