Polypyrrole molecular composites were prepared by in situ deposition in poly(ethylene oxide) complexes with copper chloride blended with polystyrene. The electrical conductivity of these materials showed some peculiar features such as anisotropy, sharp change with temperature and nonlinear I-V characteristics which were enhanced at a particular composition or certain deposition condition. These various results have been explained on the basis of phase-segregated morphology and a Poole-Frenkel type of conduction process, and are confirmed by detailed studies of the I-V characteristics.