Doug Garwood and Scott Parel joined Jimenez atop the leaderboard on the Talon Course at The TwinEagles Club. Mike Goodes had a 66, and Scott Hoch, Tommy Armour III, Bob Tway, Duffy Waldorf and Tuesday qualifier John Elliott shot 67.
Jimenez hit a 3-wood to 10 feet to set up the eagle on the par-5 sixth - his 15th hole - and made a 9-footer for birdie on the par-4 ninth.
''I played very well, very solid,'' Jimenez said. ''I make plenty of putts. Very solid from tee green. It's nice. Very happy. The condition of the golf course was excellent and not very windy.''
The Spaniard won the last of his 21 European Tour titles in 2014. He has three victories in 23 career starts on the 50-and-over tour, winning once in each of the last three seasons.
''I enjoy very much,'' Jimenez said. ''I'm 53 now. It doesn't look like it, right? But I enjoy very much. I still play some tournaments on the regular tour in Europe because I still feel like I can play there, but obviously here is a little bit more relaxing than the fighting, fighting, fighting.''
Defending champion Bernhard Langer opened with a 69. Also the Chubb Classic winner in 2011 and 2013, the 59-year-old German star won the season-opening event at Hualalai for his 30th tour victory. He has 27 rounds in a row under par.
Colin Montgomerie had a 71 for his 28th straight round under par.