After captaining Australia for the three T20s against India last month before the retiring Alyssa Healy's return for the ODI and Test, Molineux has now officially taken over.
The 28-year-old is expected to play all three T20s against West Indies in St Vincent on return from a lower-back injury, before her availability for three ODIs in St Kitts is reassessed.
But Australia have left the door open for Molineux to play as a batter only during games on this tour, with a T20 World Cup three months away and the Victorian having a long injury history.
"It's probably a see how we go," Molineux said.
"Especially towards the back end with the one-dayers. We'll just keep assessing. I am looking forward to being back out there with the girls.
"It was hard to watch that Test, especially not being part of Midge (Healy)'s last game for Australia. It will be great to get back out there again."
Not bowling would mark a significant change for Molineux, who broke into the team with her spin in 2018 and has bowled in every international she has played.
But Australia are desperate to have her around the group, with this tour the first time the squad is truly her's after Healy's retirement at the end of the home multi-format series against India.
"It's an important series for all of us," Molineux said.
"We haven't got a whole lot of games before that T20 World Cup. Each game we have together is really important and make sure we are building towards that.
"To be able to get my feet under the desk and lead the group, I am really looking forward to the opportunity."
If Molineux does not feature in the ODIs, Tahlia McGrath is in the squad alongside fellow vice-captain Ashleigh Gardner.
Australia will have some warm-up matches against South Africa before the T20 World Cup in England, which looms as crucial for the squad.
The side do not own a T20 or ODI World Cup trophy for the first time in almost a decade, after being bounced out of the semi-final stage of both the last two tournaments.
They were also beaten 2-1 at home by India in the T20s last month, but insist they are not far off the pace.it
"It's very hard in T20 cricket to play the perfect game," Molineux said.
"It's just being better for longer and realising those moments that can go either way and winning those.
"It's just backing our (attacking) style of play and being conscious of that."
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