TiO₂ (P25)-supported Au-Pd bimetal nanoparticles displayed excellent performance in the solvent-free benzyl alcohol catalytic oxidation. However, little research attention has been paid to investigate the effects of TiO₂ form on the catalytic activity of Au-Pd/TiO₂. In the present research, rutile, brookite, and anatase TiO₂ were successfully synthesized and subsequently applied as the carrier to load Au-Pd nanoparticles by the deposition-precipitation method. The experimental results indicated that the benzyl alcohol conversion employing the rutile TiO₂-supported Au-Pd catalyst is higher than the conversion of anatase and brookite TiO₂-loaded Au-Pd catalysts. However, the Au-Pd/TiO₂-rutile displayed the lowest and highest selectivity toward benzaldehyde and toluene, respectively. ICP-AES, XRD, XPS, and TEM were conducted to characterize these catalysts. The corresponding experimental results revealed that the excellent performance of Au-Pd/TiO₂-rutile catalyst was attributed to both the smaller Au-Pd nanoparticle size distribution and the higher concentrations of O_α and Pd²⁺ species on the catalyst surface. In the recycle experiments, the Au-Pd/TiO₂-rutile catalyst displayed lower reaction stability compared with the Au-Pd/TiO₂-anatase and Au-Pd/TiO₂-brookite, which might be due to the coverage of larger amount of aldehyde products on the surface.