Ruthenium nanoparticles (NPs) supported on N‐doped carbon (Ru/N−C) were prepared by the pyrolysis of cis‐Ru(phen)2Cl2 loaded onto carbon powder (VULCAN XC72R) at 800 °C. Ru/N−C NPs (0.2 mol% Ru) selectively catalyzed either acceptorless dehydrogenation coupling (ADC) or auto‐transfer‐hydrogen (ATH) reactions of amines with alcohols to imines and secondary amines. Such selectivity could be controlled by the choice of alkali metal ion associated with the base. Under similar catalytic conditions, the ADC cross‐coupling of diamines with primary alcohols or diols afforded the corresponding benzimidazoles and quinoxalines in good to excellent yields. This catalytic system displayed good activity, recyclability, and wide applicability to a diverse range of substrates.

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