But superstar allrounder Annabel Sutherland has been rested, with one eye on the Twenty20 World Cup being played in the United Kingdom from June.
Alyssa Healy's successor Molineux had captained Australia in the T20 leg of the recent multi-format series against India, before going down with the latest of many injuries across her career.
But on Tuesday Australia selectors named the 28-year-old spinner among their 15-player squad for the final series before the T20 World Cup.
The tour will include Molineux's first ODIs as full-time skipper.
"This tour marks the beginning of a new era for the side, with Sophie taking the reins across all formats and a new-look batting line-up following Alyssa's retirement," said selector Shawn Flegler.
"Sophie was terrific during the recent T20 series against India and has already begun shaping her leadership style.
"Sophie is progressing well and is expected to be available to play. We'll prioritise the T20 matches and continue to assess her across the ODI series."
Flegler said the decision to rest Sutherland was "part of a proactive management plan" that will ensure she is fit for Australia's push towards a seventh T20 World Cup title.
Big-hitting Grace Harris has been snubbed from the T20 side as Lucy Hamilton and Nicola Carey retain their spots following the India series.
Back-up wicketkeeper Tahlia Wilson will join the squad for the first time after the Women's National Cricket League final, to be played on March 21
Australia play three T20s in St Vincents from March 19, before three ODIs in St Kitts from March 27.
AUSTRALIA SQUAD:
Darcie Brown, Nicola Carey, Ash Gardner, Kim Garth, Lucy Hamilton, Alana King, Phoebe Litchfield, Tahlia McGrath, Sophie Molineux (c), Beth Mooney, Ellyse Perry, Megan Schutt, Georgia Voll, Georgia Wareham, Tahlia Wilson
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