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Abstract: Atomic force microscopy (AFM) has been used to investigate the surface structure of molecularly imprinted polyethersulphone (PES) membranes and to quantify pore size and surface roughness. Molecularly imprinted polymeric (MIP) membranes were developed using photoinitiated copolymerization of 2- hydroxyethyl methacrylate as functional monomer and trimethylopropane trimethacrylate as crosslinker in the presence of adenosine 3' : 5"-cyclic monophosphate as template, followed by deposition of a MIP layer on the surface of (PES) microfiltration membranes. Atomic force microscopy images clearly indicate that a consistent increase in the degree of modification leads to a systematic decrease in pore size and an increase in surface roughness. These results show a good correlation with the filtration data of cAMP solutions. Thus, it was shown that direct AFM quantification of key parameters of imprinted membrane structure provide useful guidelines for the development of novel MIP composite membranes. Copyright (C) 2002 John Wiley Sons, Ltd