Microplastics (MPs) in the environment pose a persistent concern, as these plastic particles can adversely impact both aquatic ecosystems and human health. MPs are subject to natural weathering and aging processes, such as photodegradation, which significantly alter their surface morphology and physicochemical properties, thereby influencing their fate, transport, and sorption behavior. To better understand how aging affects these properties and to elucidate the mechanisms behind the interactions with the chlorpyrifos pesticide, poly(ethylene terephthalate) (PET) microplastics (<100 mu m) were subjected to accelerated photoaging in a UV-B chamber for varying exposure times. Several characterization techniques were employed, including scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS), X-ray diffraction (XRD), infrared spectroscopy (IR), point of zero charge (pHPZC), and thermogravimetric analysis (TGA). Additionally, the percentage of crystallinity and carbonyl index (CI) were calculated. The results demonstrated a decrease in pHPZC following photodegradation, likely due to an increase in delta- (-C=O) groups, consistent with the CI findings. SEM revealed surface deterioration caused by aging, while TGA indicated an early thermal degradation stage associated with water volatilization, suggesting enhanced hydrophilicity. Density functional theory (DFT) calculations showed that the PET monomer absorbs slightly in the UV-B region, leading to excitation and subsequent radical reactions that form Norrish type I products. The adsorption capacity of aged PET increased compared to the pristine material, likely due to the molecular geometry becoming more planar, facilitating interactions between the aged MPs and chlorpyrifos, as confirmed by noncovalent interaction (NCI) analysis. These findings highlight the significant potential of aged microplastics to adsorb micropollutants and act as vectors in aquatic environments.