The aim of this work is to investigate the photoprotection activity and toxicity level of formulations containing the extract and its fractions obtained from leaves of Arrabidaea chica. The ex vivo percutaneous penetration of the extract was evaluated using the photoacoustic spectroscopy technique. The formulation presented optical absorption in the ultraviolet region, including UVA and UVB. This formulation was obtained without adding inorganic UV filters, as is frequently used in commercial sunscreens. The results showed a penetration rate similar to those of commercial sunscreens with its presence on the skin surface at least 180 min after the application. This formulation presented no toxic effects evaluated using hematological, biochemical, and histological assays. The results suggest that the formulation from the leaves of A. chica provides substantial protection against UVA + UVB radiation with a possible advantage of being natural and free of inorganic compounds compared with the majority of available commercial sunscreens.