The synthesis and reactivity of Mn(I) complexes bearing bifunctional ligands comprising both the amine N–H and benzimidazole fragments are reported. Among the various ligands, the N-((1H-benzimidazol-2-yl)methyl)aniline ligand containing Mn(I) complex presented higher reactivity in the transfer hydrogenation (TH) of ketones in 2-propanol. Experimentally, it was established that both the benzimidazole and amine N–H proton played a vital role in the enhancement of the catalytic activity. Utilizing this system a wide range of aldehydes and ketones were reduced efficiently. Notably, the TH of several imines, as well as chemoselective reduction of unsaturated ketones, was achieved in the presence of this catalyst. DFT calculations were carried out to understand the plausible reaction mechanism which disclosed that the transfer hydrogenation reaction followed a concerted outer-sphere mechanism.