In this paper, we report the study of a novel p-aminoazobenzene based non-conjugated, benzoxazine polymer, poly([4-(6-tert-butyl-4H-benzo[e][1,3] oxazin-3-yl) phenyl]-phenyldiazene) (AZO-PBZ) synthesized using solvent free, thermally activated cationic ring opening polymerization. The thermal, photo-physical, electrochemical, and photoconducting properties of the polymer were investigated. The optical absorption band edges of AZO-PBZ thin film was observed at 555 nm. Photoinduced charge transfer nature of AZO-PBZ was studied by analyzing the fluorescence spectra and performing photoconductivity experiments. Incorporation of [6, 6]-phenyl-C-61-butyric acid methyl ester denoted as PCBM into the polymer leads to quenching of the fluorescent intensity and exhibits significant photoconductivity. The photocurrent through the PCBM blend films was measured as a function of electric field to recognize the field dependence on carrier generation. Internal photocurrent efficiency of the polymer: PCBM blend samples was found to be in the order of 10(-5) and photoconductive sensitivity was of the order of 10(-11) S W(-1)cm, which is adequate for photorefractivity. (C) 2018 Elsevier Ltd. All rights reserved.