A mild and efficient method has been developed for the preparation of substituted coumarins from reaction of various phenols with different β-ketoesters via Pechmann condensation in the presence of Brønsted acidic ionic liquid (N-(4-sulfonic acid) butyl triethylammonium hydrogen sulfate) as an effective catalyst under solvent-free conditions. Different phenols reacted with ethyl acetoacetate to produce the corresponding substituted coumarins in high to excellent yields and short reaction times. Moreover, [TEBSA][HSO4] has been used as an effective green catalyst for the synthesis of coumarin derivatives under solvent-free conditions. Using the relatively non-toxic (halogen-free) and reusable Brønsted acidic ionic liquid, high catalytic efficiency, high yields, short reaction times and straightforward work-up are advantages of this protocol. Manuscript profile