Solid/liquid phase-transfer catalyzed alkylation and acylation of 2-mercaptobenzimidazole at 25°C by different organohalogen reagents in the presence of tetrabutylammonium bromide as a catalyst underwent, exclusively, S-monoalkylation and N-monoacylation or S-and N-dialkylation, cycloalkylation, and S-and N-diacyla-tion depending on the nature of alkylating and acylating agents.