Researchers have focused on improving the performance of polymeric membranes through various methods, such as adding inorganic nanoparticles into the matrix of the membranes. In the present study, the separation of oxygen, nitrogen, methane and carbon dioxide gases by PVC/silica nanocomposite membranes was investigated. Silica nanoparticles were prepared via sol-gel method. Membranes were prepared by thermal phase inversion method and characterized using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermal gravimetry (TGA) analyses. The FTIR and SEM analyses demonstrated a nano-scale dispersion and good distribution of silica particles in the polymer matrix. According to TGA results, thermal properties of PVC membranes were improved and DSC analysis showed that glass transition temperature of nanocomposite membranes increased by adding silica particles. We concluded that the permeability of carbon dioxide and oxygen increased significantly (about two times) in the composite PVC/silica membrane (containing 30 wt% silica particles), while that of nitrogen and methane increased only 40 to 60 percent. Introducing 30 wt% silica nanoparticles into the PVC matrix, increased the selectivity of CO2/CH4 and CO2/N2 from 15.9 and 21 to 18.2 and 27.3, respectively. The diffusion and solubility coefficients were determined by the time lag method. Increasing the silica mass fraction in the membrane increased the diffusion coefficients of gases considered in the current study.