Hydrodynamic cavitation reactors are of great promise for the applications of chemical process intensification and water treatment. In this work, a novel cylindrical rotational hydrodynamic cavitation reactor (CRHCR) with rectangular grooves and oblique tooth protrusions on the rotor surface was studied. The three-dimensional characterization of cavitation within the CRHCR was observed from the front and left views by the high-speed camera experiments. Interestingly, a new phenomenon of simultaneous formation of the attached cavitation and shear cavitation was found in the CRHCR. The synergistic effect of attached cavitation and shear cavitation contributes to the enhancement of the cavitation performance of CRHCR. In addition, the evolution of attached cavitation is explored. It is found that attached cavitation forms a trapezoidal-shaped cavitation cloud in the groove, which undergoes three various stages: incipient, development, and collapse. Finally, the pulsation frequency and cavitation intensity of shear cavitation in the chamber were investigated. The results show that the cavitation pulsation frequency is the same at the same rotational speed in the chamber near diverse oblique teeth. As the rotational speed increases, the cavitation pulsation frequency increases linearly. These findings in this paper are of great benefit to understanding the mechanism of the cavitation effect of CRHCR.