Molineux takes over from Alyssa Healy, who will retire in March, with Ash Gardner elevated to share the vice-captaincy with incumbent Tahlia McGrath.
"I have found a real passion for helping people," Molineux told reporters on Thursday.
"And I look at that Australian team and what we have now, and we have got generational talent at both ends of the scale.
"And to be able to bring all that together, that is the beauty and the really exciting part for me moving forward ... bringing it all together and seeing if we can go to new heights."
The 28-year-old Victorian takes over the captaincy with Australia ranked No.1 in the world in all formats - Test, 50-over and Twenty20.
But Molineux was cognisant Australia had failed to win the past two World Cups, in 50-over and T20 cricket.
"We have lost the last two World Cups that we have been a part of and we're not going to shy away from that," she said.
"They hurt. And we have spent time in reflection.
"I think we have just got the right ingredients to go to another level, and that's what we're all excited about.
"It's going to take a bit of courage. We're not defending anymore, we have to go out there and get it ourselves.
"And that's a really exciting place to be - and we haven't been in that place for a long time."
Born in Bairnsdale in Victoria's Gippsland region, Molineux has played 38 T20 internationals, 17 ODIs and three Tests in a career pockmarked by injury.
A foot problem kept her out of the national team for two years from 2021, and a knee injury sidelined her for the 2024-25 Ashes series.
"It has probably given me greater perspective," Molineux said of her injuries.
"Things are never as bad as they seem in the moment, or as good sometimes.
"That might keep me a bit more consistent and calm in moments. I know we're going to have a lot of big moments coming up that we're going to need that calmness."
Molineux, who has skippered Victoria since 2022 and led the Melbourne Renegades to their sole WBBL title in 2024, was approached by Cricket Australia to toss her cap in the captaincy ring just before Christmas.
McGrath and Gardner were other chief contenders.
"Why not give it a crack," Molineux said of her reaction when approached.
"I have always enjoyed leadership, always enjoyed the opportunities that I have had leading teams, starting at the Melbourne Renegades and Victoria.
"It's a real passion for me.
"And in this Australian space, there's a lot of us that haven't had titles over the years or anything like that.
"But I do really care about that team and have always thought about how we can be better and how we can keep dominating world cricket."
Molineux will take the reins for a three-match T20 series against India starting on February 15, with three 50-over clashes to follow, before a one-off Test against the Indians in Perth from March 6.
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