4-hydroxycoumarin 2a and 4-hydroxy-6-methyl-pyran-2-one 2b were applied in a one-pot reaction with Baylis-Hillman adduct acetates 1 to form novel 3-benzylpyrano [3, 2-c] pyran-2, 5-diones 3 in high yields (70-85%). The synthesized framework is available in many biologically active moieties. The reaction was carried out under dierent conditions to achieve optimum conditions. The results indicated that Et3N, as a base under solvent-free conditions, was optimum. The reaction procedure and puri cation method are mild and straightforward.