In this study, efficient, high-precision grinding of cemented carbide alloys using a specific grinding wheel was performed, and the ground surface characteristics were investigated in detail. The results showed that final finishing using a chromium-bonded wheel produced an extremely smooth surface with an average roughness Ra of 4 nm. The grinding process produced a chromium- and copper-rich surface layer, as well as a large amount of diffusion of oxygen. Adhesive strength tests using a microscratching method were also carried out on ground substrates coated with diamond-like carbon (DLC) films. The surface ground by the chromium-bonded wheel exhibited superior adhesive strength due to its strong chemical affinity with the DLC film.