We report on controlling the optoelectronic properties of self-assembled intercalating compound of graphene oxide (GO) and HCl doped polyaniline (PANI). Optical emission and X-ray diffraction studies revealed a secondary doping phenomenon of PANI with -OH and -COOH groups of GO, which essentially arbitrate the intercalation. A control on the polarity and the magnitude of the photoresponse (PR) is harnessed by manipulating the weight ratios of PANI to GO (viz., 1: 1.5 and 1:2.2 are abbreviated as PG1.5 and PG2.2, respectively), where +/-PR=100(R-Dark -RUV-Vis)/ R-Dark and R corresponds to the resistance of the device in dark or UV-Vis illumination. To be precise, the PR from GO, PANI, PG1.5, and PG2.2 are +34%, -111%, -51%, and +58%, respectively. (C) 2015 AIP Publishing LLC.