The photoelectric characteristics and paramagnetic properties of newly synthesized polyimides (PI) have been investigated using the electrophotographic method and an ESR signal study. The polyimides based on N,N,N',N'-substituted p-phenylenediamine and dianhydrides, were prepared via polycondensation. The polymers exhibit excellent solubility in common organic solvents, and have high thermal stability. The PI films exhibit photoelectric sensitivity in the UV, and visible spectral regions. The mechanism of photogeneration has been investigated.