In this paper, a novel SO3H-containing ionic liquid namely N,N-diethyl-N-sulfoethanaminium hydrogen sulfate ([Et3N–SO3H]HSO4) has been synthesized, and characterized by studying its FT-IR, 1H NMR, 13C NMR and mass spectra. Afterward, catalytic activity of the Brønsted acidic ionic liquid has been examined for the preparation of 3,4-dihydropyrimidin-2-(1H)-ones and 3,4-dihydropyrimidin-2-(1H)-thiones via the one-pot multicomponent reaction between arylaldehydes, β-ketoesters and urea (or -thiourea) under solvent-free conditions. The results showed that [Et3N–SO3H]HSO4 was highly efficient catalyst for this reaction.