Aliphatic PNP pincer-supported earth-abundant manganese­(I) dicarbonyl complexes behave as effective catalysts for the acceptorless dehydrogenative coupling of a wide range of alcohols to esters under base-free conditions. The reaction proceeds under neat conditions, with modest catalyst loading and releasing only H2 as byproduct. Mechanistic aspects were addressed by synthesizing key species related to the catalytic cycle (characterized by X-ray structure determination, multinuclear (1H, 13C, 31P, 15N, 55Mn) NMR, infrared spectroscopy, inter alia), by studying elementary steps connected to the postulated mechanism, and by resorting to DFT calculations. As in the case of related ruthenium and iron PNP catalysts, the dehydrogenation results from cycling between the amido and amino-hydride forms of the PNP-Mn­(CO)2 scaffold. For the dehydrogenation of alcohols into aldehydes, our results suggest that the highest energy barrier corresponds to the hydrogen release from the amino-hydride form, although its value is close to that of the outer-sphere dehydrogenation of the alcohol into aldehyde. This contrasts with the ruthenium and iron catalytic systems, where dehydrogenation of the substrate into aldehyde is less energy-demanding compared to hydrogen release from the cooperative metal–ligand framework.