In very cold and sometimes windy conditions at Diamond Country Club, the Spaniard carded an eagle and four birdies with a single dropped shot to get to five under.
There was then 14 European Tour wins in the group a shot back, with two time Major Champion Martin Kaymer, two time winner in 2020 John Catlin and former Italian Open champion Rikard Karlberg at four under alongside South African Jacques Kruyswijk.
Cañizares was of one the European Tour's most consistent performers for a decade after winning just his fourth event in 2006 as an affiliate member, adding the Trophée Hassan II in 2014 either side of a win at the 2009 Qualifying School.
The 38-year-old has become something of a specialist at the Q School when required, winning again in 2018 and claiming the third card in 2019, and arrived in Atzenbrugg after a top 20 last time out at the Kenya Savannah Classic supported by Absa in his 350th European Tour event, where he had also held the 18 hole lead.
"I'm very pleased," he said. "It was tough to keep focus - it's so cold. It was tough to feel the hands and that's very important.
"I think the strength was just keeping my head on every shot because it's very easy when you miss a shot to let it go on days like this when you're struggling physically and mentally to keep warm.
"It was just do my process and do every shot and I was happy the way I managed bad shots because I didn't let them get to me like has happened in the past. That was the key.
"I didn't think that I played wonderfully tee to green, it wasn't beautiful, but I hit some really good shots and I made some good putts in the end, so a solid round overall."
German Kaymer got off to a fast start from the tenth, birdieing the 11th and 12th and adding another gain on the 15th before bogeying the 17th.
Playing in the group ahead, Catlin turned in 35 with a birdie on the 13th, and while Kaymer kept his foot down making gains on the first, third and fourth, the American was in hot pursuit as he saved par after finding water on the first and picked up shots on the second, fourth and fifth.
It wasn't beautiful, but I hit some really good shots and I made some good putts in the end, so a solid round overall
A Kaymer bogey on the sixth then left the duo in a tie at the top of the leaderboard as the later starters went out in conditions which were still very cold.
Swede Karlberg birdied the fourth, eighth and tenth before dropping a shot with a three putt on the 11th.
He birdied the par five 15th but looked set to give the shot straight back on the next before holing a remarkable monster putt.
An approach to ten feet on the 17th then put him in a share of the lead but Cañizares was putting together an impressive round of his own.
After eagling the par five fourth thanks to a second to five feet, he holed a very long putt at the seventh and then picked up another shot from 25 feet on the next to share the lead and turn in 32.
He played an excellent bunker shot on the 12th but missed a short putt before regaining a share of top spot after spinning his approach to close range on the 13th.
A vicious lip out at the 15th saw him stay at four under but he played a brilliant third out of the rough for a birdie on the next before making impressive par saves from outside ten feet on the closing two holes.
Kruyswijk was a late finisher and he made birdies on the fourth, fifth, 13th, 15th and 17th to go with a dropped shot on the 11th.