This invention involves a composition, a method of making, and an application of high plasticization-resistant chemically cross-linked polymeric membranes such as cross-linked cellulose acetate (CA) membrane. These cross-linked polymeric membranes with covalently interpolymer-chain-connected rigid networks showed no decrease in CO2/CH4 ideal selectivity under 690 kPa (100 psig) pure CO2 pressure and also no CO2 plasticization up to 3447 kPa (500 psig) pure CO2 pressure. By using the method of chemical cross-linking as described in this invention, the separation characteristics of the polymeric membranes can be decisively improved. These new cross-linked polymeric membranes can be used not only for gas separations such as CO2/CH4 and CO2/N2 separations, O2/N2 separation, olefin/paraffin separations (e.g. propylene/propane separation), iso/normal paraffins separations, but also for liquid separations such as pervaporation and desalination.