'It is always nice to see your name at the top of the leaderboard,' said Jimenez, an eight-time winner on the European Tour. 'I am hitting it well and hope I stay there for the rest of the tournament.'
Reigning Volvo PGA Championship winner Ignacio Garrido used a birdie on the closing hole to complete a round of 67 and join Damien McGrane and Terry Price in a tie for second place at 8-under-par 136. Overnight leader Peter Lawrie was one shot further back at 7-under-par 137 along with Ian Woosnam.
Jimenez, who titled earlier this season at the Johnnie Walker Classic, played the back side first at Le Meridien and jumped out of the gate with a birdie at the 10th, his first.
The Spaniard added a birdie at the 16th and reached 6 under with a birdie at the first. Jimenez continued his push for the lead at the par-5 fifth and landed his third shot inside four feet.
Jimenez ran home the birdie putt and took the outright lead two holes later at the seventh.
The 40-year-old knocked his approach to nine feet at the par-4 and drained the birdie putt. Jimenez kept on rolling on the following hole and dropped his second shot within 12 feet of the cup for his sixth birdie of the day.
'The conditions were very nice today,' said Jimenez. 'There was no wind on the front nine and just a little breeze on the back nine.'
Garrido began his move up the leaderboard with an eagle at the par-5 fifth and back-to-back birdies from the sixth.
The 32-year-old bogeyed the ninth and dropped another shot with a bogey at the 13th. Garrido came right back, however, and birdied two straight starting at the 14th to climb to 7 under.
Garrido had a chance to join his compatriot Jimenez in the lead at the par-5 last and played his second shot on the green inside 13 feet. Garrido's birdie try failed to find the bottom of the cup but he settled for a birdie to finish one shot back.
Lawrie, last year's rookie of the year on the European Tour, started on the 10th and birdied his first two holes to maintain the early lead.
The Irishman found trouble with a bogey at the 13th and came back to the field with a bogey at the 17th.
Lawrie countered with a birdie at the second and followed with a birdie at the fifth. He failed to get up and down from a greenside bunker for a bogey at the sixth but managed to recover again at the par-3 eighth after almost holing his tee shot.
He tapped in for birdie to get back to 8 under but stumbled with a bogey at the ninth, his last, to finish two shots off the pace heading into the weekend.
'The course was there for the taking today but I made too many bogeys,' said Lawrie, who carded a 71. 'My iron play hasn't been too good so I need to work on that. But I didn't shoot myself in the foot like I normally do. Hopefully today was the bad day.'
Steve Webster improved his position drastically with a 66 on Friday. The Englishman moved to 6-under-par 138 to join Nicolas Colsaerts, Jean-Francois Remesy, Jarmo Sandelin, Matthew Cort, Louis Oosthuizen and Emanuele Canonica in a tie for seventh.
The 36-hole cut fell at 1-under-par 143 with 74 players making the weekend. Thomas Levet and Paul McGinley were among those who failed to qualify.