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We demonstrate that electrochemical‐induced decarboxylation enables reliable post‐polymerization modification and degradation of polymers. Polymers containing N‐(acryloxy)phthalimides were subjected to electrochemical decarboxylation under mild conditions, which led to the formation of transient alkyl radicals. By installing these redox‐active units, we systematically modified the pendent groups and chain ends of polyacrylates. This approach enabled the production of poly(ethylene‐co‐methyl acrylate) and poly(propylene‐co‐methyl acrylate) copolymers, which are difficult to synthesize by direct polymerization. Spectroscopic and chromatographic techniques reveal these transformations are near‐quantitative on several polymer systems. Electrochemical decarboxylation also enables the degradation of all‐methacrylate poly(N‐(methacryloxy)phthalimide‐co‐methyl methacrylate) copolymers with a degradation efficiency of >95 %. Chain cleavage is achieved through the decarboxylation of the N‐hydroxyphthalimide ester and subsequent β‐scission of the backbone radical. Electrochemistry is thus shown to be a powerful tool in selective polymer transformations and controlled macromolecular degradation. [ABSTRACT FROM AUTHOR]