Considering the relatively poor surface and subsurface quality of workpieces that are ground by coarse-grained grinding wheels, the nanosecond ultraviolet laser micro-structuring of coarse-grained diamond grinding wheels and the grinding performance of micro-structured grinding wheels were investigated in this study. In addition, the effect of two processing sequences on the topographical characteristics of the grooves and the effect of the groove angle ( α ) on the surface roughness ( R a ) of the ground workpiece were explored. Furthermore, the surface quality of workpieces that were ground by micro-structured (V-shaped and W-shaped patterns) and non-structured diamond grinding wheels and the grinding ratio ( G ) of the grinding wheels were comparatively analyzed. The results demonstrate the following: Compared with the grinding wheel that was subjected to micro-structuring followed by sharpening, the surface of the grinding wheel that was subjected to sharpening followed by micro-structuring had a more integral groove structure. Neither an overly large α nor an overly small α was favorable for improving the surface quality of the workpiece that was ground by a micro-structured grinding wheel. When α  = 60°, the minimum R a of the workpiece was attained. The R a of the workpieces that were ground by the grinding wheel with a V-shaped pattern (grinding wheel A) was 17–31% less than the R a of the workpieces that were ground by the non-structured grinding wheel (grinding wheel C). The R a of the workpieces that were ground by the grinding wheel with a W-shaped pattern (grinding wheel B) was 32–41% less than the R a of the workpieces that were ground by grinding wheel C. The grinding performance of the micro-structured grinding wheels was related not only to the geometric parameters of the grooves but also to the micro-structure pattern. The W-shaped pattern was superior to the V-shaped pattern in terms of cooling and chip removal. Grinding wheel A and grinding wheel B had similar abrasion resistance, which were 26% less and 23% less than the abrasion resistance of grinding wheel C, respectively.