The recent widespread use of microplastics (MPs), especially in pharmaceuticals and personal care products (PPCPs), has caused significant water pollution. This study presents a UV/electrically co-facilitated activated persulfate (PS) system to co-degrade a typical microplastic polyvinyl chloride (PVC) and an organic sunscreen -aminobenzoic acid (PABA). We investigated the effect of various reaction conditions on the degradation. PVC and PABA degradation was 37% and 99.22%, respectively. Furthermore, we observed alterations in the surface topography and chemical characteristics of PVC throughout degradation. The possible degradation pathways of PVC and PABA were proposed by analyzing the intermediate products and the free radicals generated. This study reveals the co-promoting effect of multiple mechanisms in the activation by ultraviolet light and electricity.