The utilization of readily available and non-toxic water by photocatalytic water splitting is highly attractive in green chemistry. Herein we report that light-induced oxidative half-reaction of water splitting is effectively coupled with reduction of organic compounds, which opens up, for the first time, an avenue to use water as an electron donor to enable reductive transformations of organic substances. The used photocatalyst (Pd/g-C3N4*) was synthetized by a novel method where Pd/g-C3N4 was irradiated by light in the presence of Na2CO3 and H2O. The present strategy allowed a series of aryl bromides to undergo the reductive coupling to provide biaryl products in low to high yields. Preliminary mechanistic investigation suggests that the reaction proceeds through the single electron transfer from Pd to aryl bromides. This work will guide chemists to use water as a reducing agent to develop green procedures for various organic reactions.