The removal of the phenolic compound, caffeic acid, by photodegradation has been investigated using carbon-doped titanium dioxide particles as a photocatalyst under visible light. UV−vis absorption spectroscopy and gas chromatography−ion trap mass spectrometry analyses revealed a substrate concentration dependence of the removal of caffeic acid from a water solution. The k2 and t0.5 parameters of each reaction were calculated by fitting kinetics data to a second-order kinetic adsorption model. To evaluate the photodegradation event, the effect of the adsorption process on the whole degradation was also monitored in the absence of light. Adsorption isotherm studies supported by ζ potential and scanning electron microscopy data demonstrated the pivotal role of the absorption mechanism. It was found that the whole photodegradation process is governed by a synergic mechanism in which adsorption and photodegradation are involved. This study, centered on the removal of caffeic acid from aqueous solutions, highlights the potential application of this technology for the elimination of phenolic compounds from olive mill wastewater, a fundamental goal in both the agronomical and environmental fields.