Former Australian international all-rounder Hopes has signed a two-year contract and replaces long-serving Greg Shipperd, who was axed earlier this year.
Shipperd was dropped one year into a two-year contract extension despite taking the Sixers to the BBL final against Perth last season.
Across his 11-season tenure, Shipperd guided the men in magenta to eight consecutive finals series and back-to-back titles in 2019-20 and 2020-21.
They are the second-most successful franchise in Big Bash history with three titles, behind the Scorchers with six.
Shipperd also left his post as head coach of the NSW men's team, replaced by former Test wicketkeeper Brad Haddin.
Hopes lands his first head coaching role and will move from his position as bowling coach for Indian Premier League outfit Punjab Kings and Major League Cricket team Washington Freedom.
The incoming Sixers coach represented Australia in 84 ODIs and 12 T20s, and played for the Queensland Bulls from 2000 to 2016.
"I'm incredibly honoured to join the Sydney Sixers, a club with a proud history and a strong identity built on consistency, competitiveness and connection with its fans," Hopes said in a statement.
"I'm excited to work with a talented playing group and contribute to the next phase of the Sixers' success in the BBL."
Cross-city rivals Sydney Thunder are also on the lookout for a new coach after parting ways with Trevor Bayliss in February following a last-place finish this season.
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