The two-dimensional black phosphorous (2D BP) was synthesized by a novel cryo-mediated liquid-phase exfoliation (LPE). 2D Black phosphorous/2D carbon nitride (2D BP/2D C3N4) as a dual-functional photocatalyst for efficient hydrogen evolution with the simultaneous photodegradation of bisphenol A (BPA) organic pollutants has been designed and synthesized. The as-prepared 5% 2D BP/2D C3N4 sample shows the best photocatalytic hydrogen production rate of 259.04 mu mol.g(-1).h(-1) and BPA degradation rate of 88% under light irradiation, which derives from the strong electronic coupling between 2D BP and 2D C3N4, the matched band structure and high charge mobility of 2D BP and 2D C3N4. This work provides an effective way for achieving the removal of organic pollutants from wastewater coupled with the simultaneous generation of fuel energy.