In summary, we develop a family of photopolymerizable and reprocessible network polyimides as an alternative to aromatic polyimides such as Kapton® in electronic substrate applications. We synthesized custom diallyl bisimide monomers that participate in thiol-ene photopolymerization and characterization of the resulting polymer networks reveal suitable mechanical strength, thermal stability, thermal conductivity, and dielectric properties, which compare well to commodity polyimides. This framework offers a solution to the growing e-waste problem, since we demonstrate mild depolymerization using transesterification reactions permit the selective removal of the substrate and recovery of still functional electrical components. Most importantly, this photopolymer system integrates well into existing commercial workflows and offers unique advantages towards dense, multilayered circuitry. The chemical feedstocks of such precursors further suggest economic scaling. Thus, we believe this work presents a significant step forward in the development of environmentally friendly materials for electronic applications, contributing to the efforts aimed at addressing the escalating e-waste crisis while maintaining the performance standards required by the industry.