A mild and efficient method for the chemoselective synthesis of 7-aryloyl-5. H-pyrano[3,2-c:5,6-c']diquinoline-6,8(7. H,9. H)-diones, representing a new class of substituted pyranodiquinolinone derivatives, via the annulation of arylglyoxalmonohydrates with 2,4-dihydroxyquinoline in the presence of catalytic DBU is described. The salient features of this procedure are high chemo- and regioselectivity, short reaction times, good to high yields, easy work-up, and operational simplicity.