LAUSR

The high‐value recycling of waste polyvinyl chloride (PVC) constitutes a pivotal challenge in the plastic circular economy. This study proposes a strategy to convert PVC waste into high‐performance single‐atom catalysts (SACs) through a melamine self‐assembly‐assisted pyrolysis protocol. Melamine facilitates the formation of supramolecular assemblies with HCl encapsulating PVC particles, which anchor metal ions through coordination interactions, achieving homogeneous mixing of carbon, nitrogen, and metal precursors. As a self‐sacrificing template, melamine directs the carbonization of PVC to enhance the carbonization yield and tailor the porosity. This method enables the production of various SACs (Ni, Co, Fe, Cu, Mn, and Pd), demonstrating broad applicability. As prepared Ni SACs exhibited excellent CO2 reduction performance, achieving a CO Faradaic efficiency of 98% at −0.8 V versus RHE with no activity decay after 10 h. Co SACs delivered a nitrobenzene hydrogenation turnover frequency of 94 h−1 (aniline selectivity >99%), significantly outperforming its nanoparticle counterparts. This work not only provides a novel route to the valorization of PVC waste but also establishes a universal platform for developing cost‐effective, high‐performance SACs.