This paper describes new reactions of 2,2-bis(trifluoromethyl)oxirane (1). Ring opening of 1 by oxygen, nitrogen, sulfur or carbon nucleophiles (Nu -) proceeds regioselectively, with exclusive formation of tertiary alcohols: NuCH 2 C(CF 3 ) 2 OH. The reaction of 1 with strong acids (HX) is also regioselective and proceeds under mild conditions leading to the formation of XCH 2 C(CF 3 ) 2 OH (X = FSO 2 O, CF 3 SO 2 O, Cl, I). The addition of acetic acid to 1, however, requires an elevated temperature and TaF 5 a catalyst. Highly selective reactions of 1 with nucleophilic or electrophilic reagents provide a simple and general route to materials containing CH 2 C(CF 3 ) 2 OH group.