Oxidative cross-coupling reactions between two nucleophiles have become one of the most important tools to construct chemical bonds in organic synthesis methodology.Directly using hydrocarbons to synthesize valuable chemicals is an ideal and economical process because hydrocarbons are cheap,abundant and readily available.The account covered a brief introduction about our efforts on the development of oxidative cross-coupling reactions.We discovered this reaction model by the cross-coupling of two organometallic reagents.Related mechanisms were revealed by the char-acterization of reaction intermediates and the study of reaction kinetics through operando spectroscopy,such as in-situ IR (infrared),EPR (electron paramagnetic resonance),Raman and XAS (X-ray absorption) spectroscopy.Representative applications,such as oxidative cross-coupling reactions with H2 evolution,exhibited their high atom economy and step economy.