Gas permeation and separation characteristics of ozone treated polysulfone (PSF) membranes were investigated. The PSF is one of the most widely used commercial membranes. Ozone treatment of the PSF membrane was performed for certain hours by continuously supplying 5 vol.% ozone-containing oxygen to the chamber, in which the membrane samples were charged. The permselectivity of PSF increased with ozone treatment time, and it was found that one and half hour was enough to ozone treatment. Increase in the selectivity of the membrane for He/$N_2$, HY$N_2$, O:J$N_2$, COJ$CH_4$ by ozone treatment was found to be due to decrease in the permeability of gases with larger molecular size such as $N_2$ and $CH_4$ The decrease in the permeability of gases with smaller molecular size was negligible. The increase in the selectivities of the PSF by ozone treatment would be due to decrease in the free volume of the polymer because of the oxygen complexes generated by the reaction between ozone and the polymer.