Electronic waste recycling is a recognized global challenge that requires new strategies to bind and release critical materials selectively, such as cobalt present in lithium-ion batteries. To address this challenge, hierarchical 3D-printed porous polymer scaffolds bearing supramolecular receptors were prepared using vat photopolymerization and their cobalt binding profiles were examined as a function of matrix polarity. By combining high-resolution digital light processing (DLP) with polymerization-induced phase separation (PIPS), functional acrylic copolymer networks with micrometer-level precision of geometry and nanometer-level pores were generated. Covalent integration of a methacrylate-functionalized bisdicyclohexyl acetamide (BDCA-MA) receptor enabled binding and release of cobalt(II) chloride (CoCl2) via a solvent polarity switch mechanism involving a change in solvent from ethanol to water. The present structures proved reusable as shown by sustained high binding efficiency over five bind and release cycles. This platform represents a "green" and energy conscious method for future electronic waste recycling.