This research delves into fabricating a CuO/Fe2O3/ZnO (CFZ) ternary composite photocatalyst, employing grape extract for its eco-conscious synthesis. The method intricately integrates copper acetate, ferric nitrate, and zinc acetate as precursor compounds, harmonizing them with grape extract serving as a green reducing agent. Meticulous microwave treatment and controlled calcination orchestrate the nuanced formation of the desired composite material. The extensive characterization, involving X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), energy-dispersive X-ray spectroscopy (EDXS), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area analysis, ultraviolet–visible diffuse reflectance spectroscopy (UV-DRS), and photoluminescence (PL) spectroscopy, unveils an array of favorable physical, chemical, and optical attributes conducive to proficient photocatalysis. Notably, CFZ–10mc showcases a narrower bandgap of 1.91 eV, which is pivotal for bolstering electron–hole separation, thereby enhancing its photocatalytic efficacy. Assessment of CFZ's performance in degrading Rhodamine B (RhB) under UV irradiation highlights an impressive 88.8% degradation efficiency within 120 min, accompanied by a kinetic rate constant of 1.81 × 10−2 min−1. Deliberation upon crucial parameters, including photocatalyst dosage, initial RhB pH, and reactor energy consumption, introduces the electrical energy per order (EEO) as a notable efficiency metric. CFZ manifests a substantial reduction in operational costs, estimated to be 18.10 times lower than conventional photolysis, signifying an EEO value of 509.17 kWh m−3 order−1. Optimal operational conditions propose a photocatalyst content of 1.5 g L−1 and an initial RhB pH of 7, fostering the prevalence of the primary active species, •OH. These findings illuminate CFZ's potential in mitigating organic pollutants, underlining its pivotal role in sustainable water remediation. Additionally, practical implementation guidelines for leveraging CFZ's capabilities in real-world applications are presented with care and consideration.