Solar light with high-energy ultraviolet (UV) radiation acting on the surface of cement-based materials easily changes the properties of cement-based materials by affecting their carbonation reaction. In order to elucidate the difference in the carbonation process under UV radiation in cement-based materials with different supplementary cementitious materials (SCMs), the carbonation depth (apparent pH values), chemical composition (XRD, FTIR, and TG analysis), and mechanical properties (compressive strength and microhardness) of cement-based materials were evaluated. The results revealed that UV radiation acting on the surface of cement-based materials accelerated the carbonation reaction, which enhanced the decrease rate of pH and formation of stable calcite, thereby improving the macromechanical and micromechanical properties of cement-based materials. In addition, the carbonation process under UV radiation differs according to the added SCM. In particular, silica fume substantially increased the carbonation of cement-based materials under UV radiation, resulting in a 53.3% increase in calcium carbonate coverage, a 10.0% increase in compressive strength, and a 20.9% increase in mean microhardness, whereas the incorporation of blast furnace slag resulted in a smaller effect on UV irradiation-induced carbonation. In addition, UV radiation facilitates the crystallographic transformation process of cement-based materials containing metakaolin, resulting in more stable crystals of carbonation products. This study provides a theoretical framework and serves as an important reference for the design of cement-based materials under strong UV radiation for practical engineering applications.