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A rapid and efficient procedure for the preparation of various aryl-14H-dibenzo[a.j]xanthenes was reported.The method developed produced excellent yields via one-pot condensation of β-naphthol with various aryl-aldehydes in the presence of Keggin vanadium substituted heteropolyacid,H5PW10V2O40,as catalyst under solvent free conditions.The present methodology therefore offered several advantages but not limited to excellent yields (82％-98％),short reaction times (30-50 min),mild reaction conditioas,simple work-up,as well as the utilization of cheap and environmentally benign catalyst in the absence of organic solvents.