The influence of an electrochemical surface passivation technique (cyclic potentiodynamic polarization, CPP) on the physico-chemical surface properties of SS316LS and its subsequent response to fibronectin (Fn) and pre-osteoblasts were investigated. Contact angle and zeta-potential measurements showed that the CPP-modified surface is more hydrophilic and more positively charged than the unmodified surface. Polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) was used to investigate the interaction of Fn with both surfaces. The saturated surface concentration of adsorbed Fn was higher on the CPP-modified surface. As well, significant changes were identified in the secondary structure of Fn adsorbed on both surfaces, in comparison to its native state. This data also indicated a higher degree of Fn unfolding on the CPP-modified surface. Cell studies indicated that the attachment, proliferation and morphology of pre-osteoblasts were significantly improved on the CPP-modified surface, which was attributed to the more open conformation of Fn on the CPP-modified surface. Thus, the CPP surface passivation method was demonstrated to yield a SS316LS surface of enhanced biocompatibility.