Herein a Mn(I) catalyst bearing a redox-active phenalenyl (PLY) based ligand is reported for the efficient hydrosilylation of esters to alcohols using the inexpensive silane source polymethylhydrosiloxane (PMHS) under mild conditions. Mechanistic investigations suggest a strong ligand–metal cooperation where a ligand-based single electron transfer (SET) process initiates the reaction through Si–H bond activation.