A recent experiment has revealed that additive free ester hydrogenation by Co-pincer complexes might follow an unusual non-bifunctional mechanism, however, the detailed mechanistic pathway is missing. It has been predicted that several intermediates and transition states are involved, having their essential role in the catalytic performances. Detailed theoretical studies are therefore essential in this regard for achieving more efficient ester hydrogenation catalysts. On the basis of first principles calculations, performed over Co(PNP)/(PNN) complexes, we present here the energetics and mechanistic details, showing the distinct orientations of different possible intermediates and transition states, and find the minimum energy pathway for the conversion of esters to alcohols. In the way, we find that some intermediates must undergo structural distortion for achieving the lowest potential energy barrier which must have a severe impact on the catalytic turnover frequency.