This paper reports an effective route for the syntheses of hydroxy carbamates from the reaction of CO₂, epoxides and amines catalyzed by a Au/Fe₂O₃ catalyst. Under the optimized reaction conditions, various hydroxy carbamates were successfully synthesized with 92–98% isolated yields. The catalyst could be reused for several runs without deactivation. A plausible reaction mechanism was proposed by which the hydroxy carbamate was formed through an ammonium carbamate intermediate and the catalyst mainly promoted further nucleophilic addition between the epoxide and ammonium carbamate.