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　H　2　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　H　2　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.　©　2017　American　Chemical　Society.