Coated SS316L is a potential alternative to the graphite bipolar plates (BPPs) used in proton-exchange membrane fuel cells (PEMFCs) owing to their low manufacturing cost and machinability. Due to their susceptibility to corrosion and passivation, which increases PEMFC ohmic resistance, protective and conductive coatings on SS316L have been developed. However, coating adhesion is one of the challenges in the harsh acidic environment of PEMFCs, affecting the performance and durability of BPPs. This study compares mechanical polishing and the frequently adopted chemical etchants for SS316L: Adler’s, V2A, and Carpenter’s etchant with different etching durations and their impact on the wettability, adhesion, and corrosion resistance of a Nb-coated SS316L substrate. Contact angle measurements and laser microscopy revealed that all etching treatments increased the hydrophobicity and surface roughness of SS316L substrates. Ex situ potentiodynamic and potentiostatic polarization tests and interfacial contact resistance analysis revealed high corrosion resistance, interfacial conductivity, and adhesion of the Nb-coated SS316L substrate pretreated with V2A (7 min) and Adler’s (3 min) etchant. Increased hydrophobicity (contact angle = 101°) and surface roughness (R_a = 74 nm) achieved using V2A etchant led to the lowest corrosion rate (3.3 µA.cm⁻²) and interfacial resistance (15.4 mΩ.cm²). This study established pretreatment with V2A etchant (a solution of HNO₃, HCl, and DI water (1:9:23 mole ratio)) as a promising approach for improving the longevity, electrochemical stability, and efficiency of the coated SS316L BPPs for PEMFC application.