As one of the most important semiconductor materials, silicon (Si) has been widely used in current energy and optoelectronic devices, such as solar cells and photodetectors. However, the traditional Si p–n junction solar cells need complicated fabrication processes, leading to the high cost of Si photovoltaic devices. The wide applications of Si-based photodetectors are also hampered by their low sensitivity to ultraviolet and infrared light. Recently, two-dimensional (2D) layered materials have emerged as a new material system with tremendous potential for future energy and optoelectronic applications. The combination of Si with 2D layered materials represents an innovative approach to construct high-performance optoelectronic devices by harnessing the complementary advantages of both materials. In this review, we summarize the recent advances in 2D layered material/Si heterojunctions and their applications in photovoltaic and optoelectronic devices. Finally, the outlook and challenges of 2D layered material/Si heterojunctions for high-performance device applications are presented.