Abstract The heterogeneous catalytic reaction of H 2 O 2 with iron oxides is an important reaction for the environment since both H 2 O 2 and iron oxides are common constituents of natural and atmospheric waters. In this work, three ferrihydrites, labeled Fh-1, -2 and -3, were prepared by different procedures. Fh-1 was prepared by adding alkali solution to ferric solution under stirring. In the preparation of Fh-2, the mixing procedure of the two solutions was reversed. Fh-3 was obtained by adding alkali solution and ferric solution simultaneously into a certain amount of water. The heterogeneous catalytic reaction of H 2 O 2 with three ferrihydrites in aqueous solution was investigated in detail. The results demonstrated that the apparent reaction rate was affected by the preparation procedure of ferrihydrite besides pH, temperature and the dose of catalyst. The activation energy of the decomposition reaction of H 2 O 2 was determined to be 76.13, 59.41 and 68.05 kJ mol −1 for Fh-1, -2 and -3, respectively. The activation enthalpy of the reaction were determined to be 73.59, 56.56 and 65.76 kJ mol -1 and the activation entropy of the reaction were determined to be −69.65, −119.67 and −90.58 J mol −1 K −1 , respectively.