Zinc　titanate　(ZnTiO3)　has　recently　been　applied　in　various　areas　for　its　unique　properties.　Herein,　through　tuning　the　phase　structures　of　ZnTiO3　support,　we　synthesized　two　different　Pd-based　catalysts　for　CO　oxidative　coupling　to　DMO　and　further　investigated　their　structure-activity　relationships　for　the　first　time.　The　results　indicated　that　the　strong　metal-support　interaction　between　the　cubic　phase　ZnTiO3　and　Pd　species　leads　to　an　enriched　Pd　electronic　density　and　promotes　the　bridged　CO　adsorption.　As　a　result,　the　as-synthesized　catalyst　with　cubic　phase　ZnTiO3　performed　a　turnover　frequency　(TOF)　of　339.3　min−1,　which　was　much　higher　than　the　hexagonal　one　(226.3　min−1).　©　2022　Wiley-VHCA　AG,　Zurich,　Switzerland.