A nanostructured multiwalled carbon nanotube (CNT) and titanium dioxide composite catalyst is prepared by a modified acid-catalyzed sol–gel method. Pure anatase TiO2 and the CNT-TiO2 composite are tested in the photocatalytic degradation of four para-substituted phenols: 4-chlorophenol, 4-aminophenol, 4-hydroxybenzoic acid and 4-nitrophenol. The effect of several operational parameters on the photoefficiency of the composite catalyst is studied by using 4-chlorophenol as model compound, namely catalyst loading, pH of the medium, hydrogen peroxide concentration, substrate concentration. A relationship between the Hammett constant of each para-substituted phenolic compound and its degradability by the photocatalysts is found. The effect of the carbon phase in the catalyst is ascribed to its photosensitizer action. A clear beneficial effect is observed for the degradation of 4-aminophenol and 4-chlorophenol. For the molecules with stronger electron-withdrawing (deactivating) groups, such as 4-hydroxybenzoic acid and 4-nitrophenol, no synergy effect is observed.