The worldwide challenge of eliminating pharmaceutical contaminants requires immediate attention. Developing bio-based catalysts that are eco-friendly, reusable, and high-performance, employing starch (ST) and montmorillonite (MMT) as support, holds tremendous promise as a novel biocatalyst for pharmaceutical waste removal. In this study, a montmorillonite/α-Fe2O3/starch (MMT/α-Fe2O3/ST) bio-nanocomposite photocatalyst was successfully synthesized and used for acetaminophen (ACT) degradation under UVA-LED irradiation. The influence of operational factors, such as catalyst, ACT concentrations, and solution pH, on photocatalytic activity was examined in detail; catalyst: 0.75 g/L, pH: 7.1, leading to total ACT (10 mg/L) removal in ∼80 min. MMT/α-Fe2O3/ST showed excellent durability due to negligible Fe leaching. After four successive degradation cycles, ACT and TOC elimination efficiencies remained over 91 and 42.7 %. Compared to other anions studied, carbonate ions suppressed the most ACT degradation. Based on the radical scavenger experiments, hydroxyl and superoxide radicals and holes were involved in the MMT/α-Fe2O3/ST system. LC-MS results were used to propose ACT degradation pathways. This work illuminated the significance of biocatalysts in removing emerging pollutants from wastewater.