An efficient and novel method was developed for the synthesis of 3-sulfenyl imidazo[1,2-a]pyridines in good to excellent yields via a Cs₂CO₃ promoted direct sulfenylation of imidazo[1,2-a]pyridines. The reaction proceeds smoothly with a wide range of structurally diverse heteroarenes and disulfides. This protocol is environmentally friendly because it is free of transition-metal catalysts and utilizes aryl-substituted imidazolium-based ionic liquid rather than volatile organic solvents.