Poly(vinyl ethers) (PVEs) have many applications, such as adhesives, lubricants, and anticorrosive agents, thanks to their elastic, nonirritating, and chemically inert properties. The recycling of PVEs remains largely underexplored, and current methods lack generality towards other polymer classes. Thus, the chemical upcycling of PVE into small molecule feedstocks would provide an alternative approach to combat these current issues. Here, we report a visible light-mediated method of upcycling poly(isobutyl vinyl ether) (PIBVE) into small molecules via photooxidative degradation using chlorine or bromine radicals. PIBVE can be degraded to low molecular weight oligomers within 2 h, producing good yields of alcohols, aldehydes, and carboxylic acids. Mechanistic studies suggest that hydrogen atom transfer (HAT) from the backbone or the side chain leads to small molecule generation via oxidative cleavages. Additionally, this protocol was applied to a copolymer of poly(methyl acrylate-co-isobutyl vinyl ether) to demonstrate the preference for the degradation of polymers bearing more electron-rich C–H bonds through a judicious choice of abstraction agent. Ultimately, we show that photooxidative degradation enables the selective chemical upcycling of PVEs as a method of plastic waste valorization.