Hydroxy-iron-aluminum pillared bentonite was synthesized with ion exchange method, and its catalyst characteristics were analyzed by X-ray diffraction (XRD) and UV-vis diffuse reflectance spectra. The photo-Fenton catalytic activity of hydroxy-iron-aluminum pillared bentonite was tested under different reaction condition using azocarmine B as model pollutant under UV light. It is indicated that hydroxy-iron-aluminum pillared bentonite has high photocatalytic activity and the discoloration of azocarmine B in photo-Fenton process fits pseudo-first-order kinetic models. The mineralization way of azocarmine B was also exploited by UV-vis spectra of the azocarmine B solution in heterogeneous photo-Fenton process and analysis results.