Poly(methoxy(polyethyleneoxy)propyl-co-methacryloxypropyl) silsesquioxane membranes with different copolymer ratios were successfully fabricated via UV-induced crosslinking with mechanical stability. By selectively introducing polyethylene oxide (PEO) groups covalently bound to the ladder-structured polysilsesquioxane, we effectively suppressed the PEO crystallization, allowing for excellent CO2/H2 and CO2/N2 separation under single as well as mixed gas conditions.