An efficient, rapid, one-pot synthesis of tetrahydrobenzo[b]pyran is achieved via a three-component reaction of aldehydes, 1,3-diketone, malononitrile in 20% ethanol using anhydrous potassium phosphate as a catalyst at room temperature. The key advantages are the short reaction time, high yields, simple work-up, inexpensive catalyst and purification of products by non-chromatographic methods, i.e. by simple recrystallization from ethanol.