The microwave-assisted cleavage of C–O linkages in benzyl phenyl ether was investigated at 200 °C in the presence of ZrP or SBA-15 doped with or without metal catalyst (Pd/C or Ru/C). The total yield of phenol and benzyl alcohol from benzyl phenyl ether depolymerization with ZrP was 26.91%, while the yield of phenol reached 26.11% for that with Pd/C. Hybrid catalysts performed effectively for promoting the formation of phenol. A conversion of 85.70% was achieved with ZrP–Pd/C catalyst, and the selectivity to phenol reached 47.32%. The highest yield of phenol was obtained at 1 h, and repolymerization was remarkable at longer reaction time. Based on the reaction using phenol and benzyl alcohol as the reactants, benzyl phenyl ether might be decomposed into phenol and benzyl alcohol following with the repolymerization producing thermally stable polymers in the presence of Pd.