The Ryder Cup team mates carded 66 and are joined on six-under by another Englishman, Andy Sullivan, and Australia’s Marcus Fraser.
World number three Rory McIlroy, who began the day top of Europe’s money list and is aiming to be the continent’s top earner for a third year in four, is two shots further back on 68 after chipping in from the bunker to birdie the final hole.
Poulter did not drop a shot as he claimed three birdies on the front nine and three more after the turn.
“I took care of the par-fours and the par-threes. I just didn't really take care of the par-fives,” Poulter, 39, told reporters, after squandering three birdie opportunities, missing 15-foot putts on holes two and 18 and a four-footer on seven.
“I'm playing well. I'm just not converting all of the chances that I would expect to convert. So when I do that, I'm going to find myself with a trophy in my hand,” said Poulter, who is seeking a first tour victory since 2012.
“I would like to end the year on a win. There's a lot at stake. It is probably more pride than anything else."
Kaymer, a two-time major winner, escaped with a bogey after finding water on the par-three sixth hole, while a run of five birdies on the final eight holes was marred only by another dropped shot on 16 as the early-starting players found it easier to score low before a desert wind whipped up in the afternoon.
“I gave myself a lot of chances and I putted really well, so overall it was a very, very good round,” said Kaymer.
World number 133 Fraser is an unlikely front-runner and will hope to improve on his record of two top-10 tour finishes this year despite a bogey on the 16th which pulled him back into the chasing pack.
“I missed my drive, and going in with a three-iron, it was always going to be a bit tough,” the 37-year-old said. "The greens are that good. If you pick the right line and you hit it on line, it's going to go in.”
Italy’s Francesco Molinari is five-under, while McIlroy is one of eight players a shot further back, in a pack that also includes England's Danny Willett, the Northern Irishman's main rival to win the Race to Dubai.
The top 15 players on the tour, also known as the European money list, will share an additional $5 million based on their overall season performance.
(Reporting by Matt Smith,; Editing by Neville Dalton)
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