Environmental factors like air pollutants, radiation of the sun and stress factors such as illness, smoking, or alcohol abuse produce free radicals in the human tissue as well as in the skin. Free radicals serve as the main cause for premature skin aging. Additionally, they also contribute towards immunosuppression and the formation of skin diseases including cancer. The human organism has developed a protection system against the destructive action of free radicals by means of the antioxidant network. In the present study, the interaction of free radicals and carotenoid antioxidants in the human skin under in vivo conditions was investigated and summarized. The measurement of carotenoids in human skin was performed in vivo using resonance Raman spectroscopy.