Here, we present graphene oxide (GO)-based thin-film composite (TFC) membranes with enhanced CO2 separation performance using a surface-modified substrate for uniform GO depositions. We extensively characterized the surface properties of porous substrates to identify optimal conditions for universal and uniform GO selective layer. Our results reveal that incorporating polyvinylpyrrolidone (PVP) as a gutter layer is essential for achieving consistent and regular GO layer coating. As a result, the developed GO membranes demonstrate a CO2 permeance of 350 GPU, which is a ∼350 % improvement over the GO membranes without gutter layer, coupled with a higher selectivity for CO2/N2 and CO2/CH4 pairs. The results indicate the excellent potential for significantly enhanced CO2 separation performances with the development of suitable support membranes.