Flower color is one of the most prominent traits of rose flowers and determines their ornamental value. The color of the “Chen Xi” rose can change from yellow to red during flower blooming. In the present study, the flavonoid metabolites were investigated by the UPLC-ESI-MS/MS from the petals of four successive flower development stages under natural conditions. In total, 176 flavonoid components, including 49 flavones, 59 flavonols, 12 flavanones, 3 isoflavones, 12 anthocyanins, and 41 proanthocyanidins were identified, with some of them being detected for the first time in this study. Additionally, there were 56 compounds that showed differences among comparison groups, mainly being enriched in pathways of isoflavone, flavonoid, flavone, flavonol, phenylpropanoids, and anthocyanin. Among them, it is anthocyanins that allow the rose flower to turn red when exposed to sunlight. To verify this result, compounds from rose petal with shading treatment (S2D) was also detected but could be clearly separated from the four samples under light by clustering and principal component analyses (PCA). Consistent with low anthocyanins accumulation, the flower with shading could not turn red. Moreover, it provides a foundation for further research on the light-induced color modification of flower.