Membrane separation characteristics in the nanofiltration (NF) and reverse osmosis (RO) regions of the filtration spectrum are governed by a complex combination of both steric hindrance and surface force interactions. NF and RO membranes having surface charges show unusual selectivity behavior not predicted on the basis of physical pore size alone. Hence, practical characterizations should employ techniques to gain insight on membrane function. In this work, the separation characteristics of an anionically charged modified polyvinyl alcohol (PVA) thin-film composite membrane under different operating pressures were investigated. A qualitative measurement of the surface force interactions between solutes and membrane polymer was conducted using liquid chromatography technique. An attempt was also made to study the chlorine resistance of the composite membrane.