The degradation and recovery of waste polyurethane materials have confronted enormous challenge. Controllable degradation of polyurethane elastomer is developed via selective cleavage of Csingle bondO of urethane linkages and Csingle bondN bonds. It was founded that the selective cleavage of carbon-heteroatom bonds could be efficiently performed in 70% ZnCl2 aqueous solution. The transition metal Zn2+ coordinated with N and O atoms due to their unshared electron pairs. The Csingle bondO of urethane linkages and Csingle bondN bonds were readily cleaved using ZnCl2 as catalysts at 140 °C for 2 h. However, the Csingle bondC bonds and Csingle bondOsingle bondC of ether linkages as framework structure remain intact in the degradation process. Eventually, the high-value-added chemicals including 2,4-diaminotoluene, polytetramethylene ether glycol (PTMEG) and 3,3′-dichloro-4,4′-diaminodiphenylmethane (MOCA) were retrieved via selective cleavage of Csingle bondO of urethane bonds and Csingle bondN bonds.