The incessant accumulation of pharmaceutically active compounds (PhACs) in various environmental compartments represents a global menace. Herein, an equimolar and environmentally benign FeCoNiCuZn HEA is synthesized via a facile and scalable method, and its effectiveness in eliminating four different PhACs from aqueous matrices is rigorously examined. Attributing to its relatively low bandgap and multielement active sites, the as synthesized quinary HEA demonstrates more pronounced photocatalytic decomposition efficiency, towards tetracycline (86%), sulfamethoxazole (94%), ibuprofen (80%), and diclofenac (99%), than conventional semiconductor-based photocatalysts, under visible light irradiation. Additionally, radical trapping assays are conducted, and the dissociation intermediates are identified, to probe the plausible photocatalytic degradation pathways. Further, the end-products of FeCoNiCuZn-mediated photocatalysis are eco-friendly, and the HEA can be successfully recycled repeatedly, with no obvious leaching of heavy metal ions. Overall, the findings of this study testify the applicability of FeCoNiCuZn HEA as a visible light-active photocatalyst, for treating wastewaters contaminated with PhACs.