The 38-year-old had been assistant to Belgium boss Roberto Martinez but now makes the switch to Easter Road on a deal until the summer of 2025.
Maloney will work alongside Gary Caldwell (assistant manager), Valerio Zuddas (first-team coach and conditioning), Brian Doogan (head of technical support), David Gray (first-team coach) and Craig Samson (goalkeeping coach).
His first match in charge will be on Wednesday when the Premier Sports Cup runners-up take on Aberdeen at Easter Road in the cinch Premiership.
CEO Ben Kensell told the club website: “We are very happy to welcome Shaun as our new manager, in what is undoubtedly a very important appointment for Hibernian FC. We wanted to acquire a manager who has an attacking mentality, who is progressive, and someone who is hungry for the opportunity to build something here at this big club.
“Shaun has been the stand-out candidate throughout this process as his idea of football is completely aligned with ours and the history of this club. He believes in attacking, possession-based football, and has implemented it at the highest level with Roberto Martínez at Belgium.
“Shaun’s a young coach and this is a big opportunity for him to show what we can do. We will support him in the upcoming transfer windows to help him achieve our ambitions here."
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