Nano-sized silica/polysulfone (PSf) flat sheet asymmetric MMMs with high CO2 permeance for CO2/N2 separation were fabricated by dry/wet phase inversion method using N, N-dimethylacetamide (DMAc) and tetrahydrofuran (THF) as solvents and ethanol as additives. The results indicated that the addition of nano-silica on the polymer matrix resulted on reduced membrane performance due to void formation and particle agglomeration. Optimum membrane performance was obtained at the following fabrication parameters: 22 wt.% PSf, 31.8 wt.% DMAc, 31.8 wt.% THF, 14.4 wt.% ethanol, 20 s evaporation time, and 0 wt.% silica loading, with CO2/N2 selectivity of 15.6 and CO2 permeance of 14.2 GPU.