Richard Green and Brendon Jones combined for seven birdies and two eagles in perfect scoring conditions to lead the way ahead of Northern Ireland pair Rory McIlroy and Graeme McDowell and Scots Stephen Gallacher and Martin Laird.
Green and Jones started brightly enough with four birdies on the front nine but it was their back-nine effort that took them to the top as seven shots were picked up in six holes from the 12th.
US Open champion McIlroy wasn't at his very best but he holed a good putt at the last as he and McDowell carded seven birdies and an eagle in their nine-under 63.
The Scots ensured a tie for second place after the opening fourballs after Laird holed out from a bunker at 18.
The Netherlands and United States are a shot further back in tied fifth on eight-under.
England's high-profile pairing of Justin Rose and Ian Poulter are in touch after an opening 66 but they needed four straight birdies from the 13th to reach respectability.
Poulter tweeted later: "-6 today team England or you could say @JustinRose99 I didn't hole a thing today. Looking forward to Foursomes tomorrow."