The 28-year-old will be assisted by vice-captains Luke Breust and Dylan Moore, as the Hawks rebuild after a shaky 2022.
Sicily said he felt privileged to be given the responsibility of leading the team, after nine years in the brown and gold.
"This club has invested so much effort, love and time into me as a person first and foremost," he said.
"It's an enormous responsibility but I'm ready for the challenge and can't wait to lead this group of players."
Sam Frost, Jarman Impey and Mitch Lewis will round out a six-man leadership group this season.
CEO Justin Reeves said he was sure "these men will set the standard in 2023".
Hawthorn finished 13th on the ladder last season, with hopes a new leadership squad could give the team the boost it needs.
The side's 2022 season was also marred with explosive allegations of racism against former coaches Alastair Clarkson, now Brisbane Lions coach Chris Fagan and ex-Hawks official Jason Burt.
An independent AFL investigation is ongoing.
Phil Egan, the author of Hawthorn's cultural safety review which unveiled the racism allegations, was arrested in early February on fraud allegations.
It is alleged Egan mishandled funds during his time as manager at the Murray Valley Aboriginal Cooperative between 2010 and 2012, a claim he denies.
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