A series of 4-aryl-5,10-dihydro-4H-benzo[g]chromene-5,10-dione derivatives were synthesized by a three-component reaction with aromatic aldehyde, 2-hydroxy-1,4-dihydronaphthalene-1,4-dione, and malononitrile catalyzed by triethylbenzylammonium chloride under solvent-free conditions. The novel efficient method has the advantages of environmental friendliness, high yield, simple work-up and ease of operation.