Transition　metal　salts　were　employed　as　the　catalysts　to　improve　the　selective　degradation　of　the　α-O-4　lignin　model　compound　(benzyl　phenyl　ether　(BPE))　in　the　solvothermal　system.　The　results　concluded　that　most　of　the　transition　metal　salts　could　enhance　BPE　degradation.　Among　which,　NiSO4·6H2O　exhibited　the　highest　performance　on　BPE　degradation　(90.8%)　for　5　h　and　phenol　selectivity　(53%)　for　4　h　at　200　°C.　In　addition,　the　GC-MS　analysis　indicated　that　the　intermediates　during　BPE　degradation　included　a　series　of　aromatic　compounds,　such　as　phenol,　benzyl　methyl　ether　and　benzyl　alcohol.　Furthermore,　the　mechanisms　for　BPE　degradation　and　phenol　selectivity　in　the　NiSO4·6H2O　system　involved　the　synergetic　effects　between　the　acid　catalysis　and　coordination　catalysis,　which　caused　the　effective　and　selective　cleavage　of　the　C-O　bonds.　©　2020　The　Royal　Society　of　Chemistry.