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Gadolinium(III) trifluoromethanesulfonate (Gadolinium triflate) Gd(OTf)3 catalysed efficient Hantzsch reaction via four-component coupling reactions of aldehydes, 5,5-dimethyl-1,3-cyclohexaedione (dimedone), ethyl acetoacetate and ammonium acetate at ambient temperature was described as the preparation of polyhydroquinoline derivatives. The process presented here is operationally simple, environmentally benign and has excellent yield. Furthermore, the catalyst can be recovered conveniently and reused efficiently.