The skin is a tissue with a high metabolic activity that acts as a protective layer for the internal organs of the body. This tissue is exposed to a variety of damaging agents, including reactive oxygen species (ROS), which can lead to oxidative damage to various macromolecules, disrupting vital cellular processes and increasing mutations. A situation referred to as oxidative stress occurs when a large amount of oxidants exceeds the capacity of the antioxidant defense system. Oxidative stress is considered a contributory factor to the aging process and the pathogenesis of various skin diseases, including cancer. Several current studies seek to identify new natural compounds with properties that mitigate the harmful effects of ROS, thereby acting as blockers or suppressors of the carcinogenesis process. This review briefly presents the relationship between ultraviolet radiation, ROS, and skin damage; and summarizes the in vitro and in vivo experimental evidence of the chemopreventive effect on skin cancer of phenolic compounds from blueberries (Vaccinium spp). Although several studies addressed the topic of bioactive compounds and their activities as possible anticancer agents, none have focused on the antioxidative action and antiproliferative effects on skin cancer of phenolic compounds derived from blueberries.