Through hydrogen reduction of alkali metal chromates, chromic oxide green can be prepared by the thermal decomposition of chromium oxyhydroxide (CrOOH). It was reported that the crystal structures of CrOOH have a significant effect on the color of the chromic oxide green obtained. However, the mechanisms remain unclear and need to be systematically studied. In this work, two kinds of CrOOH with different crystal structures were prepared by aqueous hydrogen reduction of sodium chromate. The chemical composition, phase structure, and morphologies of the prepared CrOOH were characterized by chemical titration, FT-IR, XRD, and SEM. The thermal decomposition processes were discussed according to the TG-DSC results. Subsequently, CrOOH with different crystal structures were used as the raw materials to prepare chromic oxide green with different color performance. The structure and morphologies of the chromic oxide green obtained were characterized by XRD and SEM. The color performance data of chromic oxide green was reported by a Datacolor 110 colorimeter using the CIE L*a*b* (1976) colorimetric system according to the International Commission on Illumination. The results showed that the CrOOH samples prepared were of base center orthorhombic structure and trigonal structure, respectively. The morphology of the CrOOH samples was flaky and hexagonal sheet shape, respectively. Their compositions could be expressed as Cr2O3?1.49H2O and Cr2O3?1.12H2O, respectively. Compared with the chromic oxide green sample obtained by the thermal decomposition of trigonal CrOOH, the chromic oxide green sample obtained by the thermal decomposition of CrOOH with base center orthorhombic structure yielded a smaller particle size, more uniform particle size distribution, and a brighter yellower color. Finally, chromic oxide green pigments with different color performances, such as bright yellow-green, blue-green, and dark green, were obtained using different ratios of CrOOH raw materials with base center orthorhombic and trigonal structures.