In the modern era, realizing highly efficient supercapacitors (SCs) derived through green routes is paramount to reducing environmental impact. This study demonstrates ways to recycle and reuse used waste dry cell anodes to synthesize nanohybrid electrodes for SCs. Instead of contributing to landfill and the emission of toxic gas to the environment, dry cells are collected and converted into a resource for improved SC cells. The high performance of the electrode was achieved by exploiting battery-type polyoxometalate (POM) clusters infused on a reduced graphene oxide (rGO) surface. Polyoxometalate (K₅[α-SiMo₂VW₉O₄₀]) assisted in the precise bottom-up reduction of graphene oxide (GO) under UV irradiation at room temperature to produce vanadosilicate embedded photo-reduced graphene oxide (prGO–Mo₂VW₉O₄₀). Additionally, a chemical reduction route for GO (crGO) was trialed to relate to the prGO, followed by the integration of a faradaic monolayer (crGO–Mo₂VW₉O₄₀). Both composite frameworks exhibit unique hierarchical heterostructures that offer synergic effects between the dual components. As a result, the hybrid material's ion transport kinetics and electrical conductivity enhance the critical electrochemical process at the electrode's interface. The simple co-participation method delivers a remarkable specific capacity (capacitance) of 405 mA h g⁻¹ (1622 F g⁻¹) and 117 mA h g⁻¹ (470 F g⁻¹) for prGO–Mo₂VW₉O₄₀ and crGO–Mo₂VW₉O₄₀ nanocomposites alongside high capacitance retentions of 94.5% and 82%, respectively, at a current density of 0.3 A g⁻¹. Furthermore, the asymmetric electrochromic supercapacitor crGO//crGO–Mo₂VW₉O₄₀ was designed, manifesting a broad operating potential (1.2 V). Finally, the asymmetric electrode material resulted in an enhanced specific capacity, energy, and power of 276.8 C g⁻¹, 46.16 W h kg⁻¹, and 1195 W kg⁻¹, respectively, at a current density of 0.5 A g⁻¹. The electrode materials were tested in the operating of a DC motor.