Marine algae have received great attention as natural photoprotective agents due to their unique and exclusive bioactive substances which have been acquired as an adaptation to the extreme marine environment combine with a range of physical parameters. These photoprotective substances include mycosporine-like amino acids (MAAs), sulfated polysaccharides, carotenoids, and polyphenols. Marine algal photoprotective substances exhibit a wide range of biological activities such as ultraviolet (UV) absorbing, antioxidant, matrix-metalloproteinase inhibitors, anti-aging, and immunomodulatory activities. Hence, such unique bioactive substances derived from marine algae have been regarded as having potential for use in skin care, cosmetics, and pharmaceutical products. In this context, this contribution aims at revealing bioactive substances found in marine algae, outlines their photoprotective potential, and provides an overview of developments of blue biotechnology to obtain photoprotective substances and their prospective applications.