Surface treatment of metallic materials prior to the application of polymer coatings plays an important role in providing improved surface features and enhanced corrosion protection. In the current investigation, we aimed to evaluate the effect of surface treatment of newly developed TiNbZr (TNZ) alloys on the surface characteristics, including the surface topography, morphology, hydrophobicity and adhesion strength of subsequent poly(3,4-ethylenedioxythiophene) (PEDOT) coatings. The surface morphology, chemical composition, and surface roughness of both treated and coated alloys were characterized by scanning electron microscopy, energy dispersive spectroscopy, and optical profilometry, respectively. The adhesion strength of the coating was measured using a micro scratch machine. Furthermore, we also evaluated the performance of electrochemically synthesized PEDOT coatings on surface-treated TNZ alloys in terms of the surface protective performance in simulated body fluid (SBF) and in vitro bioactivity in osteoblast MG63 cells. Surface analysis findings indicated that the nature of the PEDOT coating (surface morphology, topography, wettability and adhesion strength) was intensely altered, while the surface treatment performed before electrodeposition facilitated the overall performance of PEDOT coatings as implant coating materials. The obtained corrosion studies confirmed the enhanced corrosion protection performance of PEDOT coatings on treated TNZ substrates. In vitro cell culture studies validated the improved cell adhesion and proliferation rate, further highlighting the important role of surface treatment before electrodeposition.