The 34-year-old made 24 appearances at full-back for Caldy last season, scoring twice, as the Merseysiders finished 10th in the Championship.
Hayes was looking forward to another season in the second tier, but has been enticed by the opportunity to lead his boyhood club.
He told The Rugby Paper: “Last season was one of the best I’ve had. I was going to do one more, but I saw the vacancy here and through one of my friends, who is a sponsor at Chester, I was put forward for the role.
“We went for a pint and discussed what they wanted in a coach. I spoke to my family and it seemed a no-brainer.
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