Alizarin red undergoes rapid photoassisted decomposition in air-equilibrated aqueous TiO2 dispersions under visible light radiation (λ > 420 nm). Proton NMR, chemical oxygen demand (CODCr), UV−visible, IR, GC−MS, and spin-trapping ESR spectroscopic techniques were employed to obtain details of the photodegradation of alizarin red. Peroxides and carbonyl species are the first intermediates observed during the process. The major component of the peroxides produced is H2O2, and no organoperoxides were detected. We have also confirmed that in addition to CO2 and to smaller carbonyl species the principal intermediate produced is phthalic acid, which is unable to degrade further because it does not absorb the actinic visible light radiation (λ > 420 nm). The photodegradation kinetics are discussed in terms of the Langmuir−Hinshelwood model, a case of saturation type kinetics. A mechanism for the photoassisted degradation of alizarin red mediated by TiO2 particles under visible light radiation is proposed.