An iron-modified hexagonal mesoporous silica(Fe-HMS) was prepared by sol–gel method with tetraethyl orthosilicate(TEOS), iron trichloride and template reagent of dodecyl amine(DDA) as the raw materials, and the physicochemical properties of the synthesized Fe-HMS were characterized by XRD, FT-IR, UV-Vis, ESR, TG–DTA, ESEM, TEM and nitrogen adsorption–desorption testing technology. Additionally, the catalytic performance of the Fe-HMS on the reaction of phenol hydroxylation was also investigated. The results showed that the Fe-HMS prepared was spherical small particles with stable hexagonal mesoporous structure, and the irons were embedded into the frameworks of the HMS. Furthermore, the Fe-HMS exhibited a higher catalytic activity in the hydroxylation reactions of phenol, and the highest conversion ratio of phenol reached 46.9%. The catalyst could be regenerated after calcined at 450℃ for two hours. The conversion of phenol still could reach 36.4% even after seventh cycle.