In this study, sonochemically prepared (S) Pd catalysts supported on anatase (Ana) and rutile (Rut) were compared to incipient wetness impregnated (I) Pd catalysts for the direct synthesis of hydrogen peroxide. Pd/Ana-S and Pd/Rut-S achieved higher H-2 conversion than Pd/Ana-I and Pd/Rut-I due to the improvement of metal dispersion by the sonochemical method. Especially, Pd dispersion on Pd/Rut-S was estimated to be six times higher than other catalysts, resulting in the highest H2O2 production rate. Through multiple characterizations (TEM, N-2 adsorption-desorption, H-2-TPR and CO-chemisorption), we discovered that many parts of the rutile crystals were cracked during the sonochemical treatment, obtaining rectangle shape rutile crystals and two times higher specific surface area. As a result, the sonochemical method played dual-functionalities as follows: physically cracking rutile crystals and inducing small Pd nucleation by cavitation. In addition, electron-deficient Pd species, beneficial for H2O2 selectivity, were dominantly observed on rutile by XPS analysis. This outcome was explained by unstable Ti3+ species on anatase favoring the electron-rich metal. Conclusively, it is demonstrated that the sonochemical method and rutile TiO2 have a substantial synergistic effect on both H-2 conversion and H2O2 selectivity for the direct synthesis of hydrogen peroxide.