The aim of this study was to explore the potential use of silk fibroin (SF) as a catalyst support material for phenol hydroxylation reactions. Iron-substituted silk fibroin fibers were prepared using formic acid at room temperature and characterized using inductively coupled plasma atomic-emission spectrometry, scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR) and optical microscopy. Measurement of an FTIR spectrum showed that the secondary structure was beta-structure before and after iron substitution. To evaluate the catalytic properties of prepared catalyst, phenol hydroxylation reaction was carried out using aqueous hydrogen peroxide as an oxidant. An excellent transformation of phenol into dihydroxybenzenes (catechol and hydroquinone) was achieved. Phenol conversions of 3.3%, 61.2%, and 80.3% were obtained at room temperature, 40 degrees C and 60 degrees C respectively. It was found that no further phenol conversion proceeded because catalysts became separated from the reaction system during the reaction. No significant leaching of the iron was detected. Catalyst could be reused several times without a significant change in activity. Parent silk fibroin fibers without iron were inactive. (c) 2006 Society of Chemical Industry