The synthesis, characterization, and device studies of poly(benzobisoxazole imide)s containing perylene or naphthalene units in an alternating fashion with the oxazole unit are described. Photoinduced energy transfer and charge separation were studied in methanesulfonic acid (MSA) solution via absorption, excitation, and steady-state fluorescence studies. Excitation of the bisoxazole moiety resulted in enhanced emission from the perylene bisimide unit as a result of FRET (Forster resonance energy transfer). The influence of the imide substitution into the linear chain of poly(benzobisoxazole) (PBO) on its solid-state packing was examined by wide-angle X-ray diffraction (WXRD) analysis. Bottom contact field effect transistors (FET) based on thermally annealed polymer films were fabricated and studied. The polymers showed n-type charge transport and current modulation with an on/off ratio greater than 10(2). It was observed that the FETs consisting of the random copolymer of bisoxazole containing both perylene as well as naphthalene bisimide units had higher performance parameters such as better mobility (mu e) and I(on)/I(off) ratio compared to those of the pristine systems.