One of just six players to make it through all three rounds of qualifying school last year, Zions scorched Aloha Golf Club for eight birdies and one bogey to take a one-shot lead over Alejandro Canizares.
He was understandably satisfied with the round.
'It felt good -- nice and easy,' Zions said. 'Recently I've made golf more difficult than it should be instead of just picking a target and seeing where it goes.'
Canizares posted a bogey-free 66, making five birdies in his first seven holes to make the turn in 31. He had one more birdie over his next 11 holes.
'That felt really good -- and it's been a while since I could say that,' said Canizares. 'I hit a lot of nice wedges to the green and managed to knock the ball close. I've been struggling recently and my mind seems to have been somewhere else, but I feel more confident now.'
Last week's Italian Open winner, Gonzalo Fernandez-Castano, had a 5-under 67 to share third place with Chris Gane, Joakim Haeggman, Gary Lockerbie and Louis Oosthuizen.
At the 18th hole, Haeggman had a bizarre confrontation -- with a goose.
'The goose came over to me, and at first I laughed about it. But when I put my hand down it wanted to have a go at it and I had to give it a slap across the face,' Haeggman recounted. 'I had no choice.'
Elsewhere, Zions was coasting over the 6,882-yard layout without incident, aside from his bogey at the par-3 fourth. He wrapped three birdies around that misstep.
'I just switched off my brain on the greens and the ball was disappearing from everywhere,' said Zions, an Australian who lives in the United States. 'It's taken me a while to adjust to life on tour -- it can be a little intimidating out there -- but I've gone back to basics and just plugged away.'
Forty-eight of the world's top 50-ranked golfers are in the U.S. for the Players Championship.
Miguel Angel Jimenez skipped on Sawgrass to promote an event in his native Spain and opened with an even-par 72 to end the day tied for 56th place.
Fellow former Ryder Cup players Paul McGinley (71) and Lee Westwood (72) are also in the mix.