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Solar ultraviolet radiation (UVR) is a known environmental skin aggressor and main causative agent of most types of skin cancer. Skin is the physiological barrier that defends against both pathogens and chemical/physical damage. Sunlight exposure to skin may cause cellular oxidative damage and mutilation of antioxidant machinery. UVR is the key element responsible for photoageing. Photoprotection is therefore essential to avoid such undesired instances of UVR. In day to day life, the use of sunscreens has come up as the best photoprotective prerequisite. Apart from the sunscreens, special emphasis is on the use of chemicals of natural origin having photoshielding, antioxidant, radical scavenging or repair properties. Key classes of beneficial phytochemicals include phenolic acids, flavonoids, polyphenols, tea polyphenols, curcumin, resveratrol, etc. These phytochemicals are able to modulate apoptotic machinery (Bax, Caspase-3, Caspase-9, APAF-1) towards cell survival pathways (Bcl-2, PI3/AKT, mitogen-activated kinases). Several studies of medical importance have revealed that phytochemicals proceed through several molecular and cellular mechanisms to impediment or check photocarcinogenesis and photoageing. Therefore, it is very much needed to explore more photoprotective phytochemicals and understand their molecular mechanism to prevent UVR-induced damage.