Functionalized graphene quantum dot (GQD) based materials play an important role in the development of high-performance, low-cost, large-area optoelectronic devices. The progress, however, is impeded by the poor understanding of the physical mechanism for GQDs in these devices. In this paper, chlorine doped GQD (Cl-GQD) based photovoltaic photodetectors have been fabricated using a solution process, and it was found that the presence of Cl-GQDs can significantly enhance the performance of the device. The improved performance of Cl-GQD based devices has been investigated by systematically studying the structural, morphological, optical, electrical, electrochemical and photoelectrical properties. The important photovoltaic detectors parameters such as the saturation current densities (J₀), barrier heights (Φ_b), built-in potentials (V_bi), carrier concentrations (N) and depletion layer widths (W_d) have been calculated and discussed by studying the I–V and C–V characteristics under different illuminations. The frequency dependent capacitance and conductance have also been discussed. The results provide guidance for developing high-performance graphene based optoelectronic devices.