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• Direct electrochemical C2 phosphonylation of thiazole derivatives under mild conditions. • The avoidance of external metal, additive and chemical-oxidant. • Facile access to various phosphorus compounds containing multi heteroatoms. • An atom economic system with simple operation and wide substrate scope. We herein report a direct electrochemical dehydrogenative C H phosphonylation of thiazoles derivatives with H 2 evolution. Employing electricity as the green and sole oxidant, cheap metal as electrode, the anodic oxidation together with cathodic hydrogen evolution process provides a green and efficient strategy for C H phosphonylation. A diverse range of phosphorus products were constructed under external metal and oxidant-free conditions at ambient temperature, featuring atom economy, simple operation and wide reaction scope. [Display omitted] [ABSTRACT FROM AUTHOR]