The unprecedented reaction of α,β-unsaturated N-arylaldimines with two molecular 5-arylidene-1,3-dimethylbarbituric acids in methylene dichloride at room temperature afforded unique spiro[pyrido[3′,2′:5,6]pyrano[2,3-d]pyrimidine-7,5′-pyrimidines] in moderate to good yields and with high diastereoselectivity.