Carotenoids are the crucial pigments involved in photoprotection and in scavenging harmful free radicals in all living organisms. The underlying chemical processes are charge transfer and free radical reactions, both of them leading to carotenoid radical cation (Car(center dot+)) formation. Accurate knowledge of the molecular properties of Car(center dot+) is thus a prerequisite for understanding of their function as photoprotective and antioxidant agents. Despite their fundamental importance in nonphotochemical quenching in green plants, only little is known about the Car(center dot+) excited states and their dynamics. Our combined experimental and theoretical investigation employing femtosecond time-resolved pump-probe spectroscopy and quantum chemical calculations proves the existence of a second low-lying pi pi* excited-state energetically below the well-known strongly allowed excited-state responsible for the intense absorption of Car(center dot+) in the near-IR region. Hence, we suggest denoting the latter state as D-3 state in the future. Our findings have also implications for nonphotochemical quenching in green plants, since direct quenching of chlorophyll excited states by Forster energy transfer to Car(center dot+) is possible and efficient.