The metal-catalyzed hydrogenolysis of polymers is important in waste recycling; however, it is limited by the harsh reaction conditions and the low activities of catalysts, especially for earth-abundant metal-based catalysts. Herein, we perform a comprehensive study on the hydrogenolysis of polyurethane model catalyzed by Fe-, Mn-, Ru-, and Ir-iPrMACHO pincer complexes and propose a cascade mechanism comprising two-level hydrogenolysis and the hydrogenation of formaldehyde. In addition, the substrates and ligands are modulated to improve the activities of chemical recycling to monomer. It is found that the pincer ligands could dissociate from the metal centers at high reaction temperatures and further result in the deactivation of catalysts. The rigid Fe and Mn catalysts with tetradentate cyclic ligands are designed following the guidance, and the computations suggest that those designed catalysts could have high stabilities and activities.