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This paper introduces the fundamental physical characteristics of organic photovoltaic (OPV) devices. Photoelectric conversion efficiency is crucial to the evaluation of quality in OPV devices, and enhancing efficiency has been spurring on researchers to seek alternatives to this problem. In this paper, we focus on organic photovoltaic (OPV) devices and review several approaches to enhance the energy conversion efficiency of small molecular heterojunction OPV devices based on an optimal metal-phthalocyanine/fullerene (C60) planar heterojunction thin film structure. For the sake of discussion, these mechanisms have been divided into electrical and optical sections: (1) Electrical: Modification on electrodes or active regions to benefit carrier injection, charge transport and exciton dissociation; (2) Optical: Optional architectures or infilling to promote photon confinement and enhance absorption.