Benzylation of benzene has been conducted over Fe-containing zeolite molecular sieve materials prepared by different methods and exhibiting different pore sizes. It was shown that the mesoporous Fe-containing materials were very active benzylation catalysts with a monoalkylated product selectivity of 100%, and had better stability than the previously reported iron pillared clays (FePILCs). Temperature and pore size were two critical factors influencing the activities of the investigated catalysts. A redox mechanism can explain the observed experimental results.