The synthesis and development of sodium (Na)-substituted hydroxyapatite (HAp)/chitosan (CS) composite using poly (O-phenylenediamine) (PoPD) coating on 316L SS substrate for improving bioactivity and corrosion protection was studied. The surface of Na-HAp/CS/PoPD bilayer coatings on 316L SS substrate was characterized by diverse analytical techniques. The open circuit potential (OCP) measurement, potentiodynamic polarization, and impedance test revealed that the bilayer coating provides excellent protection to the substrate against the corrosion in the simulated body fluid (SBF) solution. This interior layer of the coating acts as a barrier against the release of metal ions from the substrate, which was confirmed by inductively coupled plasma-atomic emission spectroscopy. Besides, the mechanical properties of the coatings were analyzed. From the obtained results, the bilayer coating exhibited greater mechanical strength than the individual coating. An in vitro bioactivity of the coatings was assessed by immersion in the SBF solution at 7-28 days. The apatite formation of bilayer coatings on 316L SS substrate is found to be more bioactive compared with the Na-HAp, PoPD, and Na-HAp/CS. The in vitro biocompatibility test showed no adverse effects, which was proved by the enhanced biocompatibility of the bilayer coating on 316L SS. (C) 2018 Elsevier Ltd. All rights reserved.