Thermodynamics and gas transport properties of polymethylmethacrylate (PMMA) blends with polyvinylmethylether (PVME) containing various amount of poly (styrene-b-methylmethacrylate) copolymer (P(S-b-MMA)) as a compatibilizer were studied. To extract interaction energies of binary pairs involved in the blends from the phase separation temperatures using an equation-of-state theory, PVME blends with methylmethacrylate copolymers containing various amount of styrene (SMMA) were prepared. PVME formed miscible blends with methylmethacrylate copolymers containing more than 70 wt% styrene and these miscible blonds showed a LCST-type phase separation behavior. Based on the interaction information obtained here, P(S-b-MMA) copolymer was added to the PMMA/PVME blends to enhance their compatibility. The average diameter of the dispersed rubber particles was gradually decreased for the blends of containing P(S-b-MMA) from 0 to 5 phr and then leveled off at a fixed size. At a fixed bland composition, the gas permeation was also increased as the P(S-b-MMA) content increased from 0 to 5 phr and then leveled off when the P(S-b-MMA) content was higher than 5 phr.