Photo-/electrochemical catalyzed oxidative R-1-H/R-2-H cross-coupling with hydrogen evolution has become an increasingly important issue for molecular synthesis. The dream of construction of C-C/C-X bonds from readily available C-H/X-H with release of H-2 can be facilely achieved without external chemical oxidants, providing a greener model for chemical bond formation. Given the great influence of these reactions in organic chemistry, we give a summary of the state of the art in oxidative R-1-H/R-2-H cross-coupling with hydrogen evolution via photo/electrochemistry, and we hope this review will stimulate the development of a greener synthetic strategy in the near future.