We report the preparation of thermally stable spherical sulfonated aramides nanoparticles and their copper(II) complexes. Metal chelation with copper ions furnished polymeric complexes in a 1 : 2 ratio with square planar geometries as judged by their IR, UV, electron spin resonance, and elemental analysis data. The direct-current electrical conductivities demonstrated the semiconducting nature of the polymeric particles and their copper complexes. Dielectric loss analysis studies showed spectral peaks appearing at characteristic frequencies, which suggested the presence of relaxing dipoles in all of the polymers. All loss peaks were shown on a linear frequency scale and appeared in the range of 1 decade, and no overlap was observed in any of the samples, whereas in the normal polymer's dielectric loss behavior, each peak covered more than 1 decade. Moreover, the peak positions did not change with increasing temperature; this indicated a nonactivated process. The reported dielectric results revealed anomalous behavior, which has not been reported before for such polymeric analogues, as the polarization in these cases was limited by nonthermal forces, and a steady-state constant polarization was produced by an applied field. A simple method for the formation of a microporous semiconducting thin film of a polymer derived from isophthalic acid and diaminodiphenylsulfone is described. (C) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 128: 310-321, 2013