Left-armer O'Keefe, 29, was one of three spinners included for a tour expected to be played on slow pitches, and could be the 14th spinner to feature in Tests for Australia since the retirement of Shane Warne in 2007.
Among other notable selections were allrounder Glenn Maxwell and the return of batsman Phil Hughes.
O'Keefe has been long overlooked by Test selectors despite success at domestic first-class level and topped the Sheffield Shield's wicket tally last season with 41 at 20.43.
"We are unsure what pitch conditions we will encounter in the UAE but we need to be prepared to play two spinners."
Incumbent off-spinner Nathan Lyon, who has taken 112 wickets in 33 Tests at 32.99, is expected to be the front-line spinner during the tour with Maxwell offering support.
Marsh, 22, younger brother of Test batsman Shaun Marsh, gets his chance following an explosive unbeaten 86 off 69 balls with seven sixes in a one-dayer against South Africa in Harare this month.
"His form with Australia A has been fantastic and he carried that through to the recent Zimbabwe tour. If he gets his opportunity, we know he will make the most of it."
Hughes will vie with incumbent Alex Doolan for the number three spot in the Test batting order.
He will travel to the UAE earlier than his team-mates to work on his batting against spin with coaching consultant and Sri Lankan great Muttiah Muralitharan.
"Phil has been in excellent form and has been rewarded with a place in the Test squad," Marsh said. "His attitude to his game has been first rate and he thoroughly deserves this opportunity.
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