Diamond coatings possess numerous excellent properties, making them desirable materials for high-performance surface applications. However, without a revolutionary surface modification method, the surface roughness and friction behavior of diamond coatings can impede their ability to meet the demanding requirements of advanced engineering surfaces. This study proposed the thermal stress control at coating interfaces and demonstrated a novel process of precise graphenization on conventional diamond coatings surface through laser induction and mechanical cleavage, without causing damage to the metal substrate. Through experiments and simulations, the influence mechanism of surface graphitization and interfacial thermal stress was elucidated, ultimately enabling rapid conversion of the diamond coating surface to graphene while controlling the coating’s thickness and roughness. Compared to the original diamond coatings, the obtained surfaces exhibited a 63%–72% reduction in friction coefficients, all of which were below 0.1, with a minimum of 0.06, and a 59%–67% decrease in specific wear rates. Moreover, adhesive wear in the friction counterpart was significantly inhibited, resulting in a reduction in wear by 49%–83%. This demonstrated a significant improvement in lubrication and inhibition of mechanochemical wear properties. This study provides an effective and cost-efficient avenue to overcome the application bottleneck of engineered diamond surfaces, with the potential to significantly enhance the performance and expand the application range of diamond-coated components.