Human skin works as a barrier against the adverse effects of environmental agents, including ultraviolet radiation (UVR). Exposure to UVR is associated with a variety of harmful effects on the skin, and it is one of the most common health concerns. Solar UVR constitutes the major etiological factor in the development of cutaneous malignancy. However, more than 90% of skin cancer cases could be avoided with appropriate preventive measures such as regular sunscreen use. Plants, constantly irradiated by sunlight, are able to synthesize specialized molecules to fight against UVR damage. Phenolic compounds, alkaloids and carotenoids constitute the major plant secondary metabolism compounds with relevant UVR protection activities. Hence, plants are an important source of molecules used to avoid UVR damage, reduce photoaging and prevent skin cancers and related illnesses. Due to its significance, we reviewed the main plant secondary metabolites related to UVR protection and its reported mechanisms. In addition, we summarized the research in Mexican plants related to UV protection. We presented the most studied Mexican plants and the photoprotective molecules found in them. Additionally, we analyzed the studies conducted to elucidate the mechanism of photoprotection of those molecules and their potential use as ingredients in sunscreen formulas.