An unusual molecular ordering, as evidenced by number and sharpness of X-ray diffraction peaks, has been observed in electrochemically synthesized conducting copolymer of pyrrole with N -phenyl maleimide. The comonomer N -phenyl maleimide is hitherto unused in the synthesis of conducting polymers. The copolymer formation has been established by X-ray photoelectron spectroscopy. As derived from wide angle X-ray diffraction data, this novel copolymer possesses an orthorhombic structure with unit cell dimensions of a =9.28 A ̊ , b =7.1 A ̊ and c =8.4 A ̊ . From these parameters, it is inferred that the comonomers are placed in an alternate manner maintaining isotactic stereoregular conformation. Quite interestingly, this pyrrole N -phenyl maleimide copolymer, even with the absence of extended π conjugation, exhibits electrical conductivity comparable to pyrrole homopolymer itself.