Electrochemical oxidation of 2, 2, 2-trifluoroethanol (1) gave trifluoroacetaldehyde 2, 2, 2- trifluoroethyl hemiacetal (2b), which was more reactive than commercially available trifluoroacetaldehyde ethyl hemiacetal (2a). The high reactivity of 2b was utilized, for example, for the facile synthesis of 1-furyl-2, 2, 2-trifluoroethanol (4) from furan.