Carotenoids have a key role in photosynthesis in photosynthetic systems, transferring excitation energy to chlorophyll (Chi) during light harvesting. These pigments also protect the photosynthetic apparatus from photodamage by quenching the Chi triplet state and singlet oxygen. In addition, in higher plants and some algae, a number of xanthophylls also have the ability to deactivate excited Chi under conditions of excess excitation via the operation of the xanthophyll cycle (violaxanthin <----> antheraxanthin <----> zeaxanthin or diadinoxanthin <----> diatoxanthin). The formation of zeaxanthin (or diatoxanthin) can be clearly correlated with the non-photochemical quenching of Chi fluorescence, and is now recognized as a major photoprotective process in higher plants and a number of algal genera. The interconversion of these xanthophylls in response to a changing light environment alters the extent of their carbon-carbon double bond conjugation, which, in turn, affects the excited state energies and lifetimes of the carotenoids and may also alter their structure/conformation and hydrophobicity. The possible roles of these photophysical and physicochemical changes in the mechanism(s) of xanthophyll-mediated energy dissipation via quenching of Chl fluorescence are discussed.