AbstractThis paper presented an addendum rotational hydrodynamic cavitation reactors (ARHCR) that enabled circumferential shear cavitation, axial cavitation, and the Venturi effect, thus increasing cavitation efficiency. The experiments on hydroxyl (·OH) release and chemical oxygen demand (COD) removal demonstrate the feasibility of cavitation performance characterization and COD removal rate. The findings indicate that the COD removal rate can reach a maximum value of 28% or 30% with an increase in flow rate or rotating speed, respectively. Specifically, the maximum values were achieved at a rotation speed of 2,500 rpm or a flow rate of 1.0 m3·h−1. Based on the mechanism of the addendum cavitation, the wedge angles, and the crucial structural parameters, were examined for optimizing cavitation performance. The results revealed that the cavitation number and cavitation bubble were significantly influenced by wedge angles, as well as the efficiency of cavitation energy. The mechanical shear of fluid was enhanced by wedge angles, resulting in constant compression and release of fluid with increased kinetic energy. This led to stronger effects on bulge blocks, and the formation of vortexes that rebounded constantly, resulting in lower pressure areas and expanded regions of cavitation. Among the wedge angles tested, the wedge angle of 15° exhibited the highest cavitation bubbles with a maximum value of 46%. This was 31% higher than the grooves‐type cavitator reported. Furthermore, the cavitation performance was extremely improved with a wedge angle of 15°, as corresponding with the maximum efficiency of cavitation energy. These explorations provide references for the removal of COD in industrial and agricultural wastewater, as well as the development of novel reactors for wastewater treatment.