New Ni-free bulk glassy alloys in the Ti_47.5Zr_2.5+xCu_37.5−xPd_7.5Sn₅ (x=0,5,7.5) system were fabricated by copper mold casting with diameters from 1 to 3 mm, which are expected to be applied as biomaterials. The structure, thermal stability and corrosion resistance were investigated by X-ray diffraction, differential scanning calorimetry and electrochemical measurement, respectively. Surface information after immersion in Hanks’ solution was also characterized by using XPS. The results indicate that the bulk glassy alloys examined are spontaneously passivated. By anodic polarization, they show the passive current densities between 10⁻² and 10⁻³ A/m². The higher corrosion resistance for the Ti-based bulk glassy alloys is attributed to the formation of stable and protective passive films enriched with titanium and zirconium.