Insights from molecular-level mechanisms of arsenite [As(III)] and cadmium (Cd) co-adsorption on TiO2 can further our understanding of their synergistic removal in industrial wastewaters. The motivation for our study is to explore the interfacial interactions of neutrally charged As(III) and cationic Cd(2+) on nanocrystalline TiO2 using multiple complementary techniques. The results of adsorption edge, ζ potential, and surface complexation modeling suggest that coexistence of As(III) and Cd(2+) enhanced their synergistic adsorption on TiO2 and, consequently, resulted in the formation of a ternary surface complex. This ternary surface complex, in turn, inhibited the metal release into the aqueous phase and, therefore, facilitated the immobilization of the heavy metals. Our in situ flow-cell attentuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and extended X-ray absorption fine structure (EXAFS) spectroscopy evidence showed that, regardless of the order of contact, As(III) was preferentially adsorbed on TiO2 rather than Cd. In agreement with our spectroscopic analysis, quantum chemistry calculations also illustrated that the Cd-As(III)-TiO2 ternary surface complex should be formed with the adsorbed As(III) as the bridging molecule. At high As(III) concentrations, the formation of the Cd-As(III)-TiO2 complex is responsible for the Cd removal. The simultaneous removal mechanisms will further our understanding of the removal of multiple pollutants in industrial wastewaters.