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The Spaniard fired a four-under-par final round of 68 at Lake Maralen Golf Club to leapfrog overnight leaders Luke Guthrie and compatriot Rafael Cabrera Bello.
Guthrie finished two shots behind Fernandez Castaño following a one-under-par final round of 71, while Cabrera Bello slumped to a closing 73.
Francesco Molinari pulled on his golf clothing on Sunday six shots adrift of the leader, charged through the field with an eight-under par final round to finish the tournament at 10-under-par.
Molinari was joined as clubhouse leader 10-under by Thongchai Jaidee who closed with a round of 66.
However birdies for Fernandez Castaño on 15 and 17 put the Spaniard three shots clear of the field at 13-under-par, and despite a double bogey down the last he had done enough to
Fernandez Castaño's victory takes him to the top of the European Ryder Cup rankings for the event at Gleneagles next September.
Provisional European Ryder Cup Team (as of 28 Oct. 13): Gonzalo Fernandez Castaño, David Howell, Thomas Bjorn, Francesco Molinari, Henrik Stenson, David Lynn, Joost Luiten, Julien Quesne and Sergio Garcia.
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