Polysulfone membranes were modified heterogeneously by lithiation, using n-butyllithium and low concentrations of tetrahydrofuran (THF). The effects of various conditions of reactant concentration, temperature, and time were determined quantitatively. The degree of substitution was measured by XPS and FTIR, using the carbonyl absorption band of lithium-activated membranes that had been converted to ones containing acyl fluoride substituents. The optimum conditions for membrane functionalization were 0.2M n-butyllithium in hexane at room temperature. The reaction rate increased substantially in the presence of 2% THF. The surface-lithiated membranes can be derivatized, potentially with a wide variety of functional groups. © 1993 John Wiley & Sons, Inc.