Abstarct: Abstract In this research, various derivatives of polyhydroquinoline were synthesized using a supported deep eutectic solvent catalyst on a PVC-Urea-ZnCl2 substrate. The catalyst, PVC-Urea-ZnCl2, was obtained by the reaction of deep eutectic solvent on chloride/urea in a ratio of 1 to 3 with polyvinyl chloride in DMF solvent. In this method, the four-component reaction, ammonium acetate, aromatic aldehydes, ethyl acetate, and dimedone or cyclohexadione, were used under solvent-free conditions and at a temperature of 80°C in the presence of the PVC-Urea-ZnCl2 catalyst. Using this method, derivatives of substituted hydroquinolines in various positions were obtained with high yields. In the second part of this research, different derivatives of tetrahydrobenzo[b]pyran were also synthesized through a three-component reaction of dimedone or cyclohexadione, aromatic aldehydes, and malononitrile under the same conditions in the presence of the PVC-Urea-ZnCl2 catalyst. The structures of the synthesized compounds were confirmed by H-NMR, C-NMR, FT-IR analysis, as well as the catalyst structure by Fe-SEM, FT-IR, and EDS analysis.