Ferrisilicates of MFI structure (HZSM-5) with Si/Fe ratios of 27.5, 35 and 67 have been studied by in situ Mössbauer spectroscopy, and the results are correlated with studies on catalytic conversions of toluene. Various species of iron ions are identified from 300 K spectra recorded after combinations of evacuation and reduction at 570 and 670 K, respectively. The roles of identified species are suggested in catalytic processes.