Bland finished with a 12-under tally of 132, one ahead of fellow Briton Marc Warren (65), Frenchman Gregory Bourdy (64), Spain's Gonzalo Fernandez-Castano (65) and South African Garth Mulroy (67).
German Kaymer, without a victory since the WGC-Champions Tournament in China in November, was among a group of players on 136 while Ryder Cup team-mate Francesco Molinari (69) was flying the flag for Italy on 137.
Belgian Nicolas Colsaerts, the other player in the field who will represent Europe at the Ryder Cup in Illinois in two weeks' time, carded a 67 for 138.
Kaymer started his round with a hat-trick of birdies from the 10th and did not drop a stroke all day.
Bland is trying to secure his first European Tour win and needs a good week as he bids to retain his playing privileges for next season.
The 39-year-old Englishman is 126th on the money list with only the top 115 keeping their cards.
"I've had a tough couple of years but that's behind me now and I'm just trying to move forward and improve every day," Bland said.
"I don't go for the panic button which I might've done five or six years ago."