The photocatalytic degradation of aqueous solution of commercial azo textile dye, direct red 23 (DR23), was carried out in TiO2 suspension at 30°C with the use of artificial and solar light sources. The photoreaction followed the first-order behavior with respect to the azo dye as a function of irradiation time. A 2³ factorial design was carried out, in order to obtain the best experimental conditions, using the rate constant of DR23 degradation as the analytical response. Seven chemical species were determined from the normalized UV-Vis spectra during the DR23 degradation through Imbrie Q mode factor analysis followed by varimax and Imbrie oblique rotations. The addition of electron acceptors, such as H2O2, S2Os2-, and ClO3- on the optimized conditions, was carried out to increase the DR23 degradation rate. Comparison of degradation efficiencies under artificial and solar radiation was examined in the presence of oxidants.