A facile, fast, non-destructive and roll-to-roll compatible photochemical method for simultaneous partial reduction and doping of graphene oxide (GO) films through ultraviolet laser irradiation in the presence of a Cl2 precursor gas is demonstrated. The photochemical chlorinated GO-Cl films were fully characterized by XPS and Raman measurements, in which grafting of chloride to the edges and the basal plane of GO was confirmed. By tuning the laser exposure time, it is possible to control the doping and reduction levels and therefore to tailor the work function (WF) of the GO-Cl layers from 4.9 eV to a maximum value of 5.23 eV. These WF values match with the HOMO level of most polymer donors employed in OPV devices. Furthermore, high efficiency poly(2,7-carbazole) derivative (PCDTBT):fullerene derivative (PC71BM) based OPVs with GO-Cl as the hole transporting layer (HTL) were demonstrated with a power conversion efficiency (PCE) of 6.56% which is 17.35% and 19.48% higher than that of the pristine GO and PEDOT:PSS based OPV devices, respectively. The performance enhancement was attributed to more efficient hole transportation due to the energy level matching between the GO-Cl and the polymer donor.