A series of pyrano[4,3‐b]pyran derivatives have been synthesized in excellent yields by the reaction of aromatic aldehydes with malononitrile or cyanoacetate and 4‐hydroxy‐6‐methylpyran‐2‐one in water at 80 °C, with the transformation being catalyzed by an aqueous solution of thiourea dioxide(TUD). Upon completion of the reaction, the product was isolated by filtration or extraction and the remaining aqueous TUD solution could be reused several times without any discernible impact on its catalytic activity. This procedure offers several advantages over existing procedures, including high yields, operational simplicity, the use of a non‐toxic catalyst and solvent, short reaction time and minimum pollution of the environment, making it a useful and attractive process for the preparation of pyrano[4,3‐b]pyran derivatives. A series of pyrano [4,3-b] pyran derivatives have been synthesized in excellent yields by the reaction of aromatic aldehydes with malononitrile or cyanoacetate and 4-hydroxy-6-methylpyran-2-one in water at 80 ° C with the Upon completion of the reaction, the product was isolated by filtration or extraction and the remaining aqueous TUD solution could be reused several times without any discernible impact on its catalytic activity. This procedure offers several advantages over existing procedures, including high yields, operational simplicity, the use of a non-toxic catalyst and solvent, short reaction time and minimum pollution of the environment, making it a useful and attractive process for the preparation of pyrano [4, 3-b] pyran derivatives.