Preclinical, clinical and epidemiological studies suggest that exposure of skin to solar ultraviolet (UV) radiation induces harmful effects and leads to various skin diseases including melanoma and non-melanoma skin cancers. Solar UV radiation-induced skin cancers are caused by depletion in antioxidant defense system, inflammation, DNA damage, oxidation of lipids and proteins, disturbances in apoptotic machinery, deregulation of signaling pathways, mutation in critical target genes and immunosuppression. Therefore, for reducing the incidence of skin cancer the use of phytochemicals that possess the abilities to inhibit these events is gaining considerable attention as photoprotective agents. These phytochemicals are widely distributed in plant kingdom which includes fruits, vegetables, seeds, flowers and bark; and belong to several classes that include polyphenols, flavonoids, isoflavonoids, proanthocyanidins, phytoalexins, anthocyanidins and carotenoids. This chapter presents and discusses key findings from studies on the photoprotective effects of some selected phytochemicals, such as, green tea polyphenols, pomegranate fruit extract, grape seed proanthocyanidins, silymarin, resveratrol, genistein, honokiol, quercetin, delphinidin, curcumin, sulforaphone, lycopene and lutein/zeaxanthin on UV-induced skin inflammation, oxidative stress, immunosuppression, DNA damage and dysregulation of important cellular signaling pathways for the management of skin cancer.