Bernhard Langer of Germany was No. 1, followed by Seve Ballesteros, Sandy Lyle and Tom Watson.
But ominously he has lost both his singles matches with opposing captain Bernhard Langer.
Another golden oldie scoring well was Bernhard Langer, 51, the German with two past wins at Augusta.
Bernhard Langer is four shots off the lead while Jesper Parnevik is one shot further back after a 69.
She joins Seve Ballesteros, Bernhard Langer and Sergio Garcia as continental Europeans who have won the award on their own.
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There was also a moment when 55-year old Bernhard Langer, the 1993 champion, threatened as he birdied the first three holes.
Montgomerie had failed to qualify for the team, but captain Bernhard Langer had given him one of his two wild cards.
His current run of 58 cuts in a row is second in tour history to Bernhard Langer's 69 between 1991 and 1996.
Lyle was part of Europe's "Big Five" generation in the 1980s and 1990s alongside Woosnam, Nick Faldo, Seve Ballesteros and Bernhard Langer.
His performance drew fulsome praise from playing partner Bernhard Langer, Germany's greatest ever golfer, who himself carded a 72 to finish on two-under.
America's Jim Furyk, Ricky Fowler and Steve Stricker are currently tied for ninth at two-under par alongside England's Lee Westwood and two-time champion, Germany's Bernhard Langer.
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Since then Seve Ballesteros, Mark James, Sam Torrance, Bernhard Langer, Ian Woosnam and Nick Faldo have all captained Europe once before stepping aside, regardless of the result.
Kaymer is bidding to become the first German to win the Open and only the country's second major winner after Bernhard Langer won the Masters in 1985 and 1993.
Germany's Bernhard Langer claimed fourth place after a second successive 65 which left him one shot off the lead and one stroke ahead of fifth-placed Sam Torrance (67) .
Meanwhile, Sergio Garcia finished two under, Colin Montgomerie was one under, Bernhard Langer and Justin Rose fired level-par 71s and Ian Woosnam, Jose Maria Olazabal and Darren Clarke signed for 73s.
Sam will need to base his team around the experience and brilliance of Bernhard Langer, the reliability of Padraig Harrington and Darren Clarke and the youth of Sergio Garcia and Niclas Fasth.
Kaymer's runaway victory and elevation to world number two means that with Lee Westwood - who finished a lowly 64th - in top spot, Europeans hold the top two positions in the rankings for the first time since Nick Faldo and Bernhard Langer in 1993.
They were at 7-under 209 heading into a final group that figures to be as dynamic as ever, with 13 players separated by five shots, a list that includes major champions (Woods, Cabrera), aging champions (Bernhard Langer) and a half-dozen players who have been on the cusp of majors before.
Like his earlier victories in 2004 which earned him a place on Bernhard Langer's victorious Ryder Cup team, Jimenez's triumph in the second event of the 2005 campaign was built on solid play from tee to green plus an ice cool nerve when the going got tough at the end.
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