An aqueous C.I. Acid Red 2 solution was decolorized by electrolysis using iron as anode. The decolorization mechanism was investigated through experimental observations on the electrochemical behavior of C.I. Acid Red 2 on Pt rotating disk electrode, UV-visible spectra of the solution and IR spectra of the coagulated mixtures. It is found that the decolorization efficiency is high, over 98.0% after 40 min, and this high decolorization efficiency can be ascribed to the synergistic effect of electrocoagulation and electrooxidation. The electrocoagulation results from the electrogenerated iron hydroxide and the electrooxidation results from electrogenerated ferric ions. The results obtained from IR spectra shows that the decolorization of C.I. Acid Red 2 by electrooxidation is due to the partial or complete cleavage of C-N bonds in C.I. Acid Red 2.