Starc, 26, has been out of action since fracturing his foot in last November's historic day-night Test in Adelaide against New Zealand and undergoing ankle surgery.
But he has now regained fitness and leads an impressive pace attack which also features Josh Hazlewood, Nathan Coulter-Nile and John Hastings.
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"Mitchell has progressed very well in his rehab and the medical staff are confident he will be fit to play in this series," chairman of selectors Rod Marsh said.
"It is extremely pleasing to have a bowler of his calibre back in the side."
Test off-spinner Nathan Lyon, overlooked for the World T20, has been given another chance to shine in the limited-overs format after being included alongside leg-spinner Adam Zampa.
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Lyon is no stranger to conditions in the West Indies, having played five Tests and taken 23 wickets in the Caribbean where spin bowling is expected to be a major factor.
"Nathan has bowled very well in the West Indies in the past and we are predicting we will see some slow turning pitches," said Marsh.
"Adam has impressed us in India during the World T20 and has bowled consistently well, and with confidence, when given his opportunity."
The biggest surprise was the inclusion of Head in place of Shaun Marsh, who was not considered because of the impending birth of his first child.
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It is a first ODI call-up for the 22-year-old South Australian left-handed batsman who has been impressive in the domestic Big Bash League and was recently named Sheffield Shield player of the year.
"He is an exciting young batsman with a bright future and if he gets his opportunity I have no doubt he will make the most of it," said Marsh.
Australia begin the tri-series in Guyana on June 6 against South Africa before facing the hosts four days later at the same venue.
The round-robin tournament sees teams play three matches against each opponent, with the top two advancing to the final on June 26 in Barbados.
Australia squad:
Steve Smith (capt), David Warner, George Bailey, Nathan Coulter-Nile, James Faulkner, Aaron Finch, John Hastings, Josh Hazlewood, Travis Head, Usman Khawaja, Nathan Lyon, Mitchell Marsh, Glenn Maxwell, Mitchell Starc, Matthew Wade, Adam Zampa
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