Kim needed only a bogey on the par-5, 650-yard 15th after O'Hair drove into trees on the left side of the fairway and battled to a double-bogey 7.
O'Hair led after the first round of the 36-hole, four-player competition, taking a 1-stroke lead over Camilo Villegas.
Kim shot 5-under-par 66 Thursday at the Cape Kidnappers Golf Resort to post a 36-hole total of 5-under 137 to take the lead into the clubhouse.
O'Hair used a birdie at the 18th hole to tie Kim and force the playoff.
Kim collected $1 million for the victory while O'Hair settled for $500,000. Hunter Mahan, the event's defending champion, shot 2-under 140 and finished third for $300,000 while Villegas ended at 1-over and took home $200,000 for fourth place.
The Kiwi Challenge was created to determine the "best golfer under the age of 30."
Copyright 2009 by United Press International.
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