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In the present study, Cu(II) Schiff-base complex is introduced as a highly efficient and green solid catalyst for the unsymmetrical Hantzsch condensation through a four-component coupling of various aldehydes, dimedone, ethyl acetoacetate and ammonium acetate to form polyhydroquinoline derivatives in good to excellent yields. This reaction was carried out in the presence of 1 mol% of catalysts in water at room temperature. The reusability of the catalysts was demonstrated by a five-run test. Remarkable features of this new procedure are cleaner reaction profiles, shorter reactiontimes, simple experimental and work-up procedures.