Cobalt–Chrome (Co–Cr) is a biometallic alloy widely used in vivo for total joint replacement (TJR). In this study, Co–Cr was successfully electrochemically polished in terms of nanosized surface roughness and topography via an environmentally friendly and biocompatible solution based on Vitamin B4 (VB4). Voltammetry and chronoamperometry tests were used to determine optimum polishing conditions for the Co–Cr alloy, with atomic force microscopy (AFM) and scanning electron microscopy (SEM) providing surface morphology comparisons to determine the condition of electrochemical polishing. Energy dispersive X-ray analysis (EDX) combined with SEM revealed significantly smoother surfaces for each alloy surface while indicating that the elemental alloy composition ratios remained relatively unchanged before and after polishing.