Friedel-Crafts alkylation of toluene with methyl mercaptan has been investigated in the presence of H-ZSM-5 and SiO₂/H-ZSM-5 catalysts. The silica layers have been built on H-ZSM-5 zeolite by chemical liquid deposition of tetraethyl orthosilicate. The passivation with silica of the external surface of H-ZSM-5 zeolite has been confirmed by FT-IR spectroscopy and mesitylene isomerization, used as a model reaction. All catalysts exhibited notable behavior in the alkylation of toluene to xylenes. Efficiencies higher than 98 % in alkylation for both toluene and methyl mercaptan were obtained at 375 ◦C. In terms of para-selectivity, outstanding performance was revealed by the silylated zeolites. Thus, over 12% SiO₂/H-ZSM-5, at 375 ◦C and WHSV = 9.4 g_{toluene+CH3SH} g_cat^-1h¹, the para-xylene selectivity was close to 100 %. The experimental apparent activation energy for the toluene alkylation with methyl mercaptan catalyzed by H-ZSM-5 was 80 kJ/mol.