The conversion of guaiacol is examined at 300 °C in supercritical ethanol over a H 2 WO 4 catalyst. Guaiacol is consumed completely, meanwhile, 16.7% aromatic ethers and 80.0% alkylphenols are obtained. Interestingly, tert-butylphenols are produced mainly with a high selectivity of 71.8%, and the overall selectivity of 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-4-ethylphenol is as high as 63.7%. The experimental results indicate that catechol and 2-ethoxyphenol are the intermediates. Meanwhile, the WO 3 sites play an important role in the conversion of guaiacol and the Brønsted acid sites on H 2 WO 4 enhance the conversion and favour a high selectivity of the tert-butylphenols. The recycling tests show that the carbon deposition on the catalyst surface, the dehydration and partial reduction of the catalyst itself are responsible for the decay of the H 2 WO 4 catalyst. Finally, the possible reaction pathways proposed involve the transetherification process and the alkylation process during guaiacol conversion.