One ahead at halfway, the son of former Ryder Cup hero José Maria Cañizares sank birdie putts of five and seven feet on the first and third holes.
And although he then bogeyed the 405 yard fifth after bunkering his approach, defending champion Martin Kaymer had failed to find the green as well and also dropped a shot.
Cañizares stood 11 under par and Kaymer slipped into a tie for second on eight under with Australian Adam Scott, who turned in 32 with a hat-trick of birdies from the third and another at the long ninth.
Dutchman Robert-Jan Derksen and Indian Jyoti Randhawa, who eagled the third, were one stroke further back in joint fourth.
Cañizares leapt into a three-shot lead the moment he and Kaymer were back on the course.
While the Madrid golfer hit his approach to five feet and made the birdie putt, German Kaymer spun his second into the lake and bogeyed.
Jiménez remained five under after six holes and Lee Westwood went alongside him with a two-putt birdie on the long third.
By starting for home with four successive pars - that made it eight in a row - Cañizares was two ahead of Kaymer, Indian Jyoti Randhawa and Frenchman Gregory Bourdy.
Luke Donald finished with another birdie for an inward 31 and a round of 67. At seven under he still retained hopes of a second win in Europe this season.
He was alongside Ireland's Damien McGrane, who also handed in a 67, and Miguel Angel Jiménez, round in 66.