Transfer hydrogenation of azobenzene with ammonia borane mediated by pincer bismuth complex 1 was systematically investigated through density functional theory calculations. An unusual metal-ligand cooperation mechanism was disclosed, in which the saturation/regeneration of the C=N functional group on the pincer ligand plays an essential role. The reaction is initiated by the hydrogenation of the C=N bond (saturation) with ammonia borane to afford 3 CN , which is the rate-determining step with Gibbs energy barrier (ΔG ¼ 6 ) and Gibbs reaction energy (ΔG) of 25.6 and À 7.3 kcal/mol, respectively. 3 CN is then converted to a BiÀ H intermediate through a water-bridged pathway, which is followed up with the transfer hydrogenation of azobenzene to produce the final product N,N'-diphenylhydrazine and regenerate the catalyst. Finally, the catalyst could be improved by substituting the phenyl group for the tert-butyl group on the pincer ligand, where the ΔG ¼ 6 value (ratedetermining step) decreases to 24.0 kcal/mol.