This study investigated the influence of light quality (full-spectrum white vs. monochromatic red) and photoperiod (12:12 h and 16:8 h light/dark cycles) on the growth and accumulation of photoactive metabolites in Chlorella vulgaris. These metabolites are fundamental for producing ecofriendly sun protection creams and other skin products with UV protection. Cultures were grown in Bold Basal Medium under controlled conditions and analyzed using UV-Vis spectrophotometry to estimate the relative content of carotenoids and mycosporine-like amino acids. Growths with white light LED and a 16:8 h photoperiod promoted higher optical density and biomass accumulation, whereas red light induced a photoprotective response associated with greater accumulation of MAAs and carotenoids. The metabolite concentration results under red light: 153.5 ± 3.90 mg of carotenoids per gram of dry matter and 137.92 ± 6.50 mg of MAAs per gram of dry matter are higher than those found in recent literatures. These findings contribute to the design of optimized cultivation strategies for the targeted production of bioactive compounds with applications in photoprotection, cosmetics, and environmental biotechnology.