The enantioselective synthesis of (R)-salbutamol hydrochloride was investigated. The asymmetric epoxidation of 3-acetoxymethyl-4-acetyloxystyrene (1) catalyzed by chiral camphyl β-diketone iron complex enantioselectively afforded (R)-3-acetoxymethyl-4-acetyloxy styrene oxide (2) in good yield and enantioselectivity. In following steps, styrene oxide 2 was converted into (R)-salbutamol hydrochloride in 68% overall yield via the ring-opening of chiral terminal styrene oxide 2 with t-butylamine and then with hydrochloride. Some factors effecting the yield and the enantioselectivity of asymmetric epoxidation of 3-acetoxymethyl-4-acetyloxystyrene (1) were discussed.