La or Ce-containing mordenite samples were synthesized from an amine-free fluorine-containing system with a quite broad range of raw materials compositions. When cerous nitrate was used in place of lanthanum nitrate as the starting material for synthesis of the zeolite, the formation of quartz could be inhibited. Aluminum is the necessary starting material for synthesis of the rare earth-containing modemite, which features good activity for catalyzing phenol hydroxylation reaction with a less tar formation and a higher ratio of ortho-hydroxyphenol/para-hydroxyphenol. The activity of Ce-containing modemite is apparently higher than that of La-containing mordenite. The mordenite sample with high cerium content can give a higher phenol conversion coupled with a 200% increase in hydroquinone selectivity, resulting in an apparent reduction in para-benzoquinone selectivity. The phenol conversion increases in big chunks with an increasing reaction temperature, leading to an obvious reduction in para-benzoquinone selectivity along with an increasing decline ratio of ortho/para-positioned hydroxyphenol products. The appropriate hydroxylation reaction time is in the range of 4-6 hours.