Recently, Graphene Oxide (GO) has extensively studied as a membrane material due to its 2D structure and high CO2 sorption property, however, GO membrane still has challenging issues; low gas permeability to apply to practical system and low stability under dry condition. In this study, we introduced GO as a nanofiller in CO2-philic polymer matrix because GO has molecular sieving property and 2D structure. First, we mixed two kinds of PEO-containing polymers by controlling the ratio of free volume in polymer networks to increase the permeability, and then, we added GO in the mixed polymer matrix for improving the CO2/N2 selectivity. Finally, we fabricated GO-incorporated mixed matrix membranes with high CO2/N2 separation performance beyond the upper bound. High long-term stability and high CO2/N2 selectivity were also achieved in mixed gas system.