This research focuses on developing and optimizing mixed matrix membranes (MMMs) by incorporating graphene oxide (GO) into a polysulfone (PSF) matrix to enhance the separation performance of CO₂ and CH₄. The morphology and gas separation performance of the MMMs were systematically characterized. The incorporation of GO enhanced gas permeation and CO₂/CH₄ selectivity, as evaluated using a gas permeation setup. Notably, the PSF/GO-0.3 wt.% membrane exhibited superior performance, achieving a CO₂ permeability of 21.63 Barrer, among the highest reported for PSF-based MMMs. Additionally, the membrane demonstrated a CO₂/CH₄ selectivity of 14.32, highlighting its effectiveness in distinguishing between the two gases, which is essential for carbon capture and natural gas decontamination applications. The uniform distribution of GO within the polymer matrix contributed to the membrane’s enhanced performance. Furthermore, the MMMs exhibited outstanding resistance to CO₂ plasticization, with the PSF/GO-0.3 wt.% membrane maintaining its performance at pressures up to 10 bar, a significant improvement over the pristine PSF membrane, which failed at 4 bar. The improved plasticization resistance is ascribed to the reinforcing effect of GO, which stabilizes the polymer matrix, minimizing CO₂-induced swelling. The PSF/GO-0.3 wt.% membrane exhibited exceptional CO₂ permeability, selectivity, and plasticization resistance, making it a viable alternative for industrial gas separation applications and outperforming previously reported PSF-based MMMs.