The　direct　hydrogen　peroxide　(H2O2)　product　from　H-2　and　O-2　is　a　promising　anthraquinone　replacement　because　it　is　environmentally　friendly　and　has　a　high　atom　efficiency.　Experimental　and　theoretical　studies　have　proven　that　optimizing　the　adsorption　of　the　critical　intermediate　OOH*　on　the　metal　site　significantly　promotes　the　further　protonation　of　this　intermediate　and　inhibits　the　O-O　bond　cleavage,　thus　enhancing　the　activity　and　selectivity.　Redistributing　the　charge　density　of　active　sites　to　tuning　the　d-band　center　of　the　metal　could　effectively　modulate　the　intermediates　adsorption,　and　thus　regulate　the　catalytic　efficiency.　Herein,　we　show　that　a　Lewis　acid　(ZnCl2　solution)　induces　abundant　oxygen　vacancies　(Ovs)　on　the　TiO2　surface,　which　results　in　a　reversal　of　charge　transfer　from　TiO2-Ov　support　to　the　Pd　atom,　generating　an　electron-rich　Pd　configuration.　Compared　with　pristine　Pd/TiO2,　Pd/TiO2-Ov　possesses　higher　H2O2　selectivity　and　productivity,　with　values　of　80.7%　and　186　mol　kg(cat)(-1)　h(-1),　respectively.　In　addition,　Pd/TiO2-Ov　maintains　stability　during　the　six　cycles　reaction　due　to　its　high　resistance　to　the　leaching　of　Pd　species.　Theoretical　calculations　reveal　that　the　reversed　charge　transfer　downshifts　the　d-band　center　of　Pd,　which　promotes　O-2　adsorption　on　the　Pd　surface　and　weakens　the　OOH*　intermediates　adsorption.　Thus,　the　energy　barrier　for　the　hydrogenation　of　the　OOH*　intermediate　is　significantly　decreased,　and　the　O-O　band　cleavage　is　inhibited.　This　study　reports　a　reversal　of　charge　transfer　tuning　the　d-band　center　of　the　active　site　for　efficient　direct　H2O2　synthesis,　which　may　provide　insight　for　designing　high-performance　catalysts.