Water pollution with microplastics has become a significant concern. Conventional treatment methods have proven ineffective, and alternatives are being explored. Herein, we assess the degradation efficiency of polystyrene (PS) by measuring its nanosecond discharge in air in contact with water. Its discharge is characterized during processing, and a transition from streamer-like to spark-like discharge occurs due to the increased electrical conductivity of water. Experiments are conducted at different frequencies, and the highest degradation is achieved at 10 kHz; an 83% polystyrene weight loss is recorded after 5 min of processing. The optical spectra of the discharge show no evidence of C-species, and an FTIR analysis of the processed polystyrene reveals no structural modifications. An NMR analysis shows the presence of ethylbenzene in water. Finally, a mechanism of PS degradation is proposed.