An efficient and simple solvent-free procedure for the synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[<em>a</em>]-xanthen-11-one derivatives <em>via</em> the one-pot multi-component condensation of dimedone with aromatic aldehydes and β-naphthol in the presence of protic acidic ionic liquid pyrazinium di(hydrogen sulfate) {Py(HSO<sub>4</sub>)<sub>2</sub>} as a green and homogeneous catalyst is described. All reactions proceed efficiently, and the title compounds are produced in high yields and in short reaction times.
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