<p>The heterogenization of homogeneous catalysts is of paramount importance for advancing practical and industrial applications within the framework of sustainable development. Here, we have engineered a Merrifield resin-anchored dioxidotungsten(VI) catalyst (<b>PS-1</b>) by the reaction of a free functional group -OH present in complex [(W^VIO₂){Hen(3,5-dmb)₃}] (<b>1</b>) [where H₃en(3,5–dmb)₃ represents the benzoxazine ring-opened form of ligand H₂en{(3,5-dmb)₂(6,8-dmbenzox)} (<b>I</b>) with a Merrifield resin (chloromethylated polystyrene cross-linked with divinylbenzene), resulting in the polymer-supported heterogeneous catalyst, [(W^VIO₂){en(3,5-dmb)₃}]@PS (<b>PS-1</b>). Comprehensive characterization of the <b>PS-1</b> catalyst was conducted using an array of analytical and spectroscopic techniques such as FT-IR, UV-vis, TGA, FE-SEM, MP-AES, XPS and AFM. Following the successful synthesis and extensive characterization of <b>PS-1</b>, its catalytic efficacy was evaluated in the one-pot, four-component synthesis of bioactive pyranopyrazole heterocycles using ethanol as an environmentally benign solvent. Purification through a non-chromatographic method yields up to 97% of the product. The catalyst was proved highly efficient and recyclable, retaining its catalytic activity over multiple runs, thus underscoring its potential for sustainable pyranopyrazole synthesis with reduced environmental impact. A plausible mechanistic pathway for this multicomponent reaction has been proposed, substantiated by the isolation and characterization of intermediate species.</p> Graphical Abstract <p>A heterogeneous dioxidotungsten(VI) complex of aminiphenolate ligand by immobilizing on polymer has been prepared, characterized, and used as a catalyst for the one-pot, four-component synthesis of pyranopyrazoles, utilizing ethanol as a green solvent</p> <p></p>