In order to enhance the bonding strength between coatings and substrates, argon glow plasma pretreatment with various times was conducted on tantalum substrates, followed by hafnium coating deposition. The coating, consisting of deposition and a diffusion layer with nanocrystalline grains of dimensions ranging from 10 to 20 nm, obtained on the substrate pretreated for 1 h, manifested the optimal structure, with a maximum thickness of approximately 14 μm and the best adhesion performance of approximately 9.5 N. The study found that the pretreatment led to grain refinement at a depth of approximately 150 nm and an increase in the crystal face spacing of substrate and high-energy defects. In addition, the crystal defects and lightly increased surface roughness enhanced the surface energy, while the Ta (200) and Ta (211) crystal faces, which had a lower combination energy and a more stable state with Hf atoms than the Ta (110) crystal face, were considerably increased on pretreated substrates with a decrease in the Ta (110) crystal face. Consequently, coating elements exhibited enhanced diffusion within the substrate, leading to the better formation of a gradient structure, which effectively improved the adhesion of coatings. Further, this study offers an efficacious approach to enhance coating adhesion and provides a deeper understanding of plasma pretreatment.