Microplastics (MP) are synthetic polymers commonly found in various consumer products, including cosmetics and cleaning agents. Due to improper disposal, they are frequently detected in both natural and wastewater systems. Surfactants, widely used in detergent formulations, represent a significant class of pollutants in sewage. This study investigates the influence of two surfactants—Linear Alkylbenzene Sulfonate (LAS) and Polyoxyethylene sorbitan monolaurate (Tween-20)—on the removal of UV-oxidized aged microplastics via chemical coagulation. The results indicate that Tween-20 affected MP removal with an efficiency of 90%, whereas LAS achieved a removal rate of 56.15% at a surfactant concentration of 140 mg L⁻¹. The low efficiency in the presence of LAS is attributed to its anionic nature, which induces electrostatic repulsion within the system. Structural characterization of the microplastics revealed modifications following oxidation and chemical coagulation in the presence of surfactants. These changes were evidenced by reduced transmittance in Fourier-transform infrared spectroscopy (FTIR) spectral bands, increased colloidal instability as indicated by Zeta Potential (PZ) measurements, a decrease in colloidal particle size, and the formation of larger, more irregularly shaped sedimented aggregates with microporous structures, as showed in scanning electron microscopy (SEM) and Energy-Dispersive X-ray Spectroscopy (EDS).