Friedel-Crafts green allcylation of xylenes with tert-butanol was investigated in the presence of mesoporous superacidic catalysts named as UDCaT-4, UDCaT-5 and UDCaT-6. The catalysts are modified versions of zirconia showing high catalytic activity, stability and reusability. The catalytic activity is in the order: UDCaT-5 (most active) > UDCaT-6 > UDCaT-4 > sulfated zirconia (least active). Synergistic effect of very high sulfur content present (9% (w/w) S) and preservation of tetragonal phase in UDCaT-5, in comparison with sulfated zirconia (4% (w/w) S), were responsible for higher catalytic activity. The performance of UDCaT-5 in alkylation of xylenes was studied with tert-butanol with reference to selectivity and stability. Alkylation of m-xylene over UDCaT-5 gives 96% conversion of tert-butanol with 82% selectivity towards 5-tert-butyl-m-xylene (5-TBMX) under optimum reaction conditions. The formation of products is correlated with the acidity of the catalyst. The reactions were conducted in liquid phase at relatively low reaction temperatures (130-160 degrees C). A systematic investigation of the effects of various operating parameters was done to describe the reaction pathway. The reaction was carried out without any solvent in order to make the process cleaner and greener. An overall second order kinetic equation was used to fit the experimental data, under the assumption that both xylene and tert-butanol are weakly adsorbed. An independent study of dehydration of tert-butanol (TBA) was also done. Alkylation of o-xylene and p-xylene with tert-butanol was also studied. The overall process is green and clean. (C) 2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.