In the drive toward green and sustainable chemistry, exploring efficient and stable metal-free photocatalysts with broadband solar absorption from the UV to near-infrared region for the photoreduction of water to H2 remains a big challenge. To this end, a binary nanohybrid (BP/CN) of two-dimensional (2D) black phosphorus (BP) and graphitic carbon nitride (CN) was designed and used as a metal-free photocatalyst for the first time. During irradiation of BP/CN in water with >420 and >780 nm light, solid H2 gas was generated, respectively. Owing to the interfacial interaction between BP and CN, efficient charge transfer occurred, thereby enhancing the photocatalytic performance. The efficient charge-trapping and transfer processes were thoroughly investigated with time-resolved diffuse reflectance spectroscopic measurement. The present results show that BP/CN is a metal-free photocatalyst for artificial photosynthesis and renewable energy conversion.