The commercial reagent 3-hydroxo-4-(2-hydroxo-4-sulfo-1-naphthylazo)-2-naphthalenecarboxylic acid (HCC) was investigated for its potential in metal ions’ detection. The interaction of the reagent with a wide spectrum of metal ions was studied using standard analytical and spectroscopic techniques (FTIR, UV/Vis, conductivity measurements and potentiometric titration). The reagent was found to show interesting photochemical properties that promote it to be a selective detector for cerium ions in aqueous solutions. The interaction between HCC and cerium (IV) sulfate was studied by UV/Vis spectroscopy. The effectiveness of HCC reagent as a chemosensor for cerium ions in aqueous matrix was high, where its sensitivity reached a detection limit of < 0.5ppm. The results presented in this report imply a valuable recruitment of an efficient colorimetric detector for cerium ions in aqueous solutions.