Polystyrene with pendant perfluorobutylsulfonylimide (PPFSI) was developed as a novel polymer-supported strong acid catalyst for alkylation of hydroquinone (HQ) with tert-butanol (TBA), and highly selective synthesis of 2-tert-butyl hydroquinone (2-TBHQ) was investigated over PPFSI under various experiment conditions. When the molar ratio of TBA to HQ was 1.2:1, using 3 mol% of PPFSI as catalyst in 1,2-dichloroethane at 130 degrees C for 5 h, the maximum of selectivity (85.9%) of 2-TBHQ was obtained while the conversion of HQ was 76.7%. Compared with other solid acid catalysts PPFSI was found to be a very effective and reusable catalyst for alkylation of hydroquinone with tert-butanol.