Asymmetric tubular alumina-supported poly(vinyl acetate) (PVAc) and poly(vinyl pyrrolidone) (PVP) membranes were created and characterized by pervaporation separation of binary mixtures of methanol and methyl tert-butyl ether (MTBE). The active separation layer was created by free-radical graft polymerization of PVAc and PVP onto a vinylsilane-modified alumina substrate with an average native pore diameter of 50 Angstrom. The separation layer consisted of a surface phase of terminally anchored polymer chains with estimated radius of gyration about a factor of 4.5-6.8 larger than the membrane pore radius. The methanol separation factors for the PVP and PVAc-grafted pervaporation membranes reached values of 26 and 100, respectively, at the lower range of methanol concentrations (1-5% v/v) tested in the study. The separation impact of the grafted polymer chains was apparent given that the native (unmodified) and vinylsilylated alumina membranes lacked selectivity for the MTBE/methanol system. Total permeate flux attained with the PVAc and PVP-based membranes ranged from 0.055 to 1.26 and 0.55 to 6.19 kg/m(2) h, respectively, over the respective feed methanol concentration ranges of 1-90 and 5-90% (v/v). A tradeoff between separation and permeate flux was apparent from the decrease in permeation flux with increasing separation factor.