Lignin　is　continuously　investigated　by　various　techniques　for　valorization　due　to　its　high　content　of　oxygen-containing　functional　groups.　Catalytic　systems　employing　hydrolysis‑hydrogenolysis,　leveraging　the　synergistic　effect　of　redox　metal　sites　and　acid　sites,　exhibit　efficient　degradation　of　lignin.　The　predominance　of　either　hydrolysis　or　hydrogenolysis　reactions　hinges　upon　the　relative　activity　of　acid　and　metal　sites,　as　well　as　the　intensity　of　the　reductive　atmosphere.　In　this　study,　the　Pd-MoOx/TiO2　catalyst　was　found　to　primarily　catalyze　hydrolysis　in　the　lignin　depolymerization　process,　attributed　to　the　abundance　of　moderate　acidic　sites　on　Pd　and　the　redox-assisted　catalysis　of　MoOx　under　inert　conditions.　After　subjecting　the　reaction　to　240　°C　for　30　h,　a　yield　of　48.22　wt%　of　total　phenolic　monomers,　with　5.90　wt%　consisting　of　diphenols,　was　achieved.　Investigation　into　the　conversion　of　4-propylguaiacol　(4-PG),　a　major　depolymerized　monomer　of　corncob　lignin,　revealed　the　production　of　ketone　intermediates,　a　phenomenon　closely　linked　to　the　unique　properties　of　MoOx.　Dehydrogenation　of　the　propyl　is　a　key　step　in　initiating　the　reaction,　and　4-PG　could　be　almost　completely　transformed,　accompanied　by　an　over　97　%　of　4-propylcatechol　selectivity.　This　distinctive　system　lays　a　new　theoretical　groundwork　for　the　eco-friendly　valorization　of　lignin.　©　2024　Elsevier　B.V.