Abstarct: In this research, a new method is reported for the synthesis of tetrahydrobenzo[b]pyran derivatives using polyvinyl chloride supported with deep eutectic solvent include zirconium oxide/urea as an efficient heterogenous catalyst. The catalyst was prepared from the reaction of PVC with urea and zirconium oxide in DMF at 100 ºC. Multicomponent reaction of dimedone, malononitrile and aromatic aldehydes in the presence of environmentally friendly PVC/Urea/ZrO2 catalyst, produced tetrahydrobenzo[b]pyran derivatives with high yields. Also, this methodology was successfully used for the one-pot synthesis of propargyloxy derivatives of tetrahydrobenzo[b]pyran, without separating intermediates. The structure of the synthesized compounds was confirmed by HNMR, CNMR and FT-IR analysis. The catalyst structure was also confirmed by CHNS, ICP, EDX, Fe-SEM and FT-IR analysis.