Understanding the behavior of PVC microplastics under UV light and their interaction with antibiotics is critical for evaluating their environmental impact. Herein, a systematic investigation reveals the adsorption behavior of UV-aged PVC (UV-PVC) microplastics toward ofloxacin (OFX), focusing on compositional and morphological changes and their adsorption behavior post-aging for 30 days. The UV aging process increased the oxygen-to-carbon (O/C) ratio of PVC from 0.23 to 1.17, along with increased oxygen-containing functional groups (− OH, − C = O) that governed the interaction behavior leading to a significant improvement in adsorption capacity reaching 38.98 mg/g compared to 18 mg/g at equilibrium compared to pristine PVC (P-PVC). The enhanced interaction was particularly effective at neutral pH, where hydrogen bonding and electrostatic interactions were optimum as confirmed by DFT calculation. These findings contribute to profiling the environmental behavior of microplastics and assessing their role as a vector for emerging pharmaceutical pollutants.