To develop highly efficient synthetic reactions is quite important in organic chemistry. Cross dehydrogenative couplings (CDC) utilize C−H bonds of substrates to construct new C−X (X=C, S, O, N, P) bonds. For CDC, the pre‐functionalization of reaction substrates can be avoided and the C−X (X=C, S, O, N, P) bonds can be newly formed by simple and efficient synthesis routes. Meanwhile, water is increasingly used as a substitute for organic solvents in cross‐dehydrogenative coupling because of its rich content, non‐toxicity, and non‐ flammability. In recent years, organic chemists are devoted their efforts to explore the cross dehydrogenative couplings (CDC) in aqueous phase which feature high atom utilization rate and environmental friendliness. Herein, we summarized the recent advances in the construction of C−C, C−S, C−O, C−N, and C−P bonds through CDC reactions of C−H bonds in water.