Water pollution, particularly from organic contaminants like dyes, is a pressing issue, prompting exploration into advanced oxidation processes (AOPs) as potential solutions. This study focuses on synthesizing Cu2O on cellulose-based fabric using Eucalyptus globulus leaf extracts. The resulting catalysts effectively degraded methylene blue through photocatalysis under LED visible light and heterogeneous Fenton-like reactions with H2O2, demonstrating reusability. Mechanistic insights were gained through analyses of the extracts before and after Cu2O synthesis, revealing the role of phenolic compounds and reducing sugars in nanoparticle formation. Cu2O nanoparticles on cellulose-based fabric were characterized in terms of their morphology, structure, and bandgap via SEM-EDS, XRD, Raman, FTIR, UV–Vis DRS, and TGA. The degradation of methylene blue was pH-dependent; photocatalysis was more efficient at neutral pH due to hydroxyl and superoxide radical production, while Fenton-like reactions showed greater efficiency at acidic pH, primarily generating hydroxyl radicals. Cu2O used in Fenton-like reactions exhibited lower reusability compared to photocatalysis, suggesting deterioration. This research not only advances understanding of catalytic processes but also holds promise for sustainable water treatment solutions, contributing to environmental protection and resource conservation.