Abstract: By using the cheap and easily-available alcohol as the alkyl source, 10%(mol)p-toluenesulfonic acid as the catalyst, a catalytic dehydrative substitution reaction of 2-mercaptopyridine and alcohols is developed for the green and efficient synthesis of 2-pyridyl thioethers, and the yields of target thioethers are up to 95%. This solvent-free method only requires the cheap and easily-available p-toluenesulfonic acid as the catalyst and can be easily extended to the synthesis of other heteroaryl thioethers.