This study investigates the decomposition kinetics and microplastic residue formation of the polymer-coated controlled-release fertilizers (CRFs) LN40 and Eco-LN40 under simulated photodegradation conditions. Eco-LN40, containing TiO₂ as a photocatalyst, achieved complete decomposition (100 ± 2%) after 60 days of xenon-arc irradiation (p <0.05), whereas LN40 achieved only 14%–31% decomposition. Analytical characterization using TED-GC/MS, FTIR, and Raman spectroscopy confirmed that polyethylene (PE) signals completely disappeared in Eco-LN40 but persisted in LN40, indicating that microplastics did not form and that there was total oxidation into CO₂ and H₂O. SEM–EDS revealed Ti enrichment and surface fragmentation consistent with photoinduced radical oxidation. This study provides qualitative and mechanistic evidence that TiO-catalyzed photodegradation can eliminate polymer residues, mitigate the risk of microplastic contamination in agricultural soils, and support carbon-neutral fertilizer technologies.