In this article an attempt is made to review critically the papers concerning novel membrane characterization methods. In particular, our focus on Raman spectroscopy, electron spin resonance (ESR) and atomic force microscopy. For each method the general principle is briefly outlined, followed by discussions on characterization of polymeric materials, in general, and synthetic polymeric membranes, in particular. After highlighting several examples, discussions are made on advantages for each method in order to identify specific area of applications. In general, Raman Spectroscopy is most adequate to obtain information on crystalline structure of the macromolecules and, change of polymeric structure in membrane, ESR on the mobility of molecules in membrane polymer matrixes and membrane pores, and Atomic Force Microscope for three;dimensional display of membrane surfaces.