Copper-mediated reversible-deactivation radical polymerization (RDRP), particularly Atom Transfer Radical Polymerization (ATRP), is a key method for producing block copolymers with precisely defined architectures and functional groups, even in sensitive aqueous and biological environments. While the field has matured, a new wave of methodological advances has taken over and shifted the field towards more application-driven synthesis. This review focuses on the most recent breakthroughs (2020-2025) and moves from core mechanistic theories to 'next-generation' strategies like photo- and electrochemically mediated ATRP and systems that thrive despite oxygen exposure. This review also highlights how modern studies have successfully pushed metal contamination down to the ppm/ppb levels and why this is critical for biomedical and electronic integration. Beyond synthesis, we map these polymers onto their real-world roles in nanotechnology, energy devices, and other applications. Finally, remaining challenges are discussed (e.g., catalyst recovery, scalability, control with challenging monomers), and future directions are presented. • This review defines copper-mediated ATRP as a structure-property design platform. • Bridges ATRP fundamentals with recent advances and industrial deployment gaps. • Analyzes ppm/ppb copper ATRP enabling bioelectronic integration. • Correlates photo-, electro-, and oxygen-tolerant ATRP with aqueous control. • Prioritizes catalyst recovery, scalability, and monomer scope expansion.
Alsubaie et al. (2026) studied this question.