The main purpose of this research was preparation of the tannic acid-based copper nanoparticle (TAN–Cu–NP) and its use as a nanocatalyst in the synthesis of diverse polyhydroquinolines (PHQs) which are biologically important. Tannic acid was extracted from the fresh barks of the Pistacia Atlantica Desf tree which is found in the Ilam province in west of Iran. Then, the TAN–Cu–NP catalyst was prepared by a reduction reaction between tannic acid and Cu2+ ions from Cu(NO3)2 in water and characterized by FT-IR, UV–Vis, EDX, XRD, SEM and TEM. Then, the TAN–Cu–NP catalyst was applied for the green synthesis of diverse PHQs from the reaction of ethyl aceto-acetate, dimedone, ammonium acetate and benzaldehydes in ethanol under reflux conditions in high yields and low reaction times. Structures of PHQs were confirmed by spectroscopic data (IR and NMR). Since the TAN–Cu–NP catalyst is made of natural materials, it has a great advantage compared with the other catalysts.