Racemates of 1,3-butanediol, 2-butanol and their derivatives were enantioselectively separated by evapomeation (EV) and pervaporation (PV) through (+)-poly{1-[dimethyl(10-pinanyl)silyl]-1-propyne} membrane. The permeation rate (P, g m m(-2) h(-1)) and enantioselectivity (% enantiomeric excess (%ee) of the permeate) were very high. For example, the P and %ee values in EV for (+/-)-1,3-butanediol were 1.19 x 10(-3) and 41.7%ee, and those in PV for (+/-)-2-butanol were 8.37 x 10(-4) and 44.6%ee, respectively. This is the first example of vapour enantioselective permeation.