A novel nano-porous state was fabricated at the surface of the Ti-based metallic glass by selective etching technique. By transforming the surface of the Ti45Y11Al24Co20 phase separated alloy from smooth towards rough with nano-pores in an oxidised state, the passivation behaviour of the glassy alloy in simulated body fluid condition was remarkably improved leading to corrosion resistance significantly higher than that of the Ti–6Al–4V alloy, one of the favourite candidate materials for implant applications.