Rose hips are rich in various nutrients and have long been used for food and medicinal purposes. Owing to the high phenolic content, rose hips can be used as natural antioxidants. In this study, ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was used to conduct a widely targeted metabolomics analysis on the polyphenolic components of Rosa xanthina f. spontanea in three ripening stages: unripe, half-ripe and fully ripe fruit. A total of 531 polyphenol metabolites were detected, including 220 phenolic acids, 219 flavonoids, 50 tannins and 42 lignans and coumarins. There were 160 differential metabolites between unripe and half-ripe rose hips (61 downregulated and 99 upregulated) and 157 differential metabolites between half-ripe and fully ripe rose hips (107 downregulated and 50 upregulated). The results of our study not only greatly enrich the chemical composition database of rose hips but also provide metabolomics information on the changes in polyphenolic metabolism during fruit development for the first time, which will help select the optimal harvest time of rose hips to achieve better quality.