This article explores the electrochemical anodization of binderless tungsten carbide (WC) using computational simulations and experimental methods. It aims to comprehend the complex relationship between anodization time, surface roughness, elemental composition, and current behavior on polished and non-polished substrates. COMSOL Multiphysics models provide the initial findings by meticulously mapping the electrolyte's potential and the current density vectors. These simulations reveal the fundamental electrochemical behaviors anticipated during anodization, particularly emphasizing the regions near the anode expected to undergo anodization. Experimental observations confirm the simulation results, showcasing how non-polished WC surfaces, replete with inherent imperfections, undergo anodization characterized by fluctuating current densities and compositional changes, highlighting the profound influence of surface defects on electrochemical processes. On the other hand, when WC substrates are polished, they show a more consistent and controlled anodization process. This suggests a close connection between the occurrence of anodization and the surface treatment, ultimately influencing the effectiveness of anodization. This comprehensive study, which combines simulation and experimentation, greatly enhances the understanding of the electrochemical anodization of WC. It suggests potential methods for enhancing surface modifications to expand the range of applications for WC, particularly in precision glass molding, aerospace, and medical industries.