BACKGROUND: Environmentally friendly solid catalysts are important in many processes from an industrial point of view and are applied widely in the study of alkylation of phenol with methanol in gas phase. However, liquid-phase reactions have not been well studied. This paper deals with an assessment of liquid-phase electrolytic alkylation in the presence of SO42-/Fe2O3-MoO3. RESULTS: A bidentate structure was formed between the SO42- and metal. A catalyst with an amorphous structure delivered lower catalytic activity even at a higher Mo content. The highest activity was obtained at an Mo content of 16% (molar composition), which delivered a phenol conversion of up to 70.5%. Experiments also showed that the catalyst can be reused at least for three times. CONCLUSION: Application of solid catalyst in the liquid-phase reaction assisted by electrolysis alkylation was found to be viable. The main products were methoxyphenols, in contrast to that associated with gas-phase operation. A possible mechanism of product formation has been proposed. (c) 2008 Society of Chemical Industry.