A method of photoprotecting a keratinous substrate comprising applying a composition onto the keratinous substrate, the composition comprising at least one phenolic compound chosen environmental at least one ortho-diphenol, at least one phenolic compound having a carboxylic acid moiety, and mixtures thereof, —a compound chosen from at least one pelyarn!ne, at least one water solvable metal salt, and mixtures thereof; and a cosmetically acceptable carrier. The present disclosure also relates to photoprotective compositions for application onto hair and skin, the compositions comprising at least one phenolic compound chosen from at least one ortho-diphenol, at least one phenolic compound having a carboxylic acid moiety, and mixtures thereof; a compound chosen from at least one polyamine, at least one water soluble metal salt, and mixtures thereof; and a cosmetically acceptable carrier.