Postpolymerization modification offers a versatile strategy for synthesizing complex macromolecules, yet modifying acrylamide polymers like poly(N,N-dimethylacrylamide) (PDMA) is notoriously challenging due to the inherent stability and low reactivity of amide bonds. In this study, we unveil a novel approach for the direct transamidation of PDMA, leveraging recent advances in the transamidation of unactivated tertiary amide substrates. By exploiting photoiniferter polymerization, we extended this direct transamidation approach to ultrahigh-molecular-weight (UHMW) PDMA, showcasing the unprecedented postpolymerization modification of synthetic polymers exceeding 106 g/mol. We also designed acrylamide copolymers comprising both the moderately reactive N-methyl-N-phenyl tertiary amides, along with the less reactive, fully alkyl-substituted N,N-dimethyl amides inherent to PDMA. This disparate reactivity enabled a sequential, chemoselective transamidation by initially targeting the more reactive pendant aryl amides with less nucleophilic aromatic amines, and second, transamidating the untouched N,N-dimethyl amide moieties with more nucleophilic aliphatic amines, yielding a uniquely diversified acrylamide copolymer. This work not only broadens the scope of postpolymerization modification strategies by pioneering direct transamidation of unactivated amides but also provides a robust platform for the design of intricate macromolecules, particularly in the realm of UHMW polymers.