Reversible addition–fragmentation chain transfer (RAFT) polymerization has undergone transformative growth since its inception in 1998, emerging as a powerful and versatile tool for precision polymer synthesis. This review highlights the latest developments in non-traditional RAFT polymerization from 2020 to 2025, capturing major innovations in activation techniques and expanding applications. Key emerging directions include the integration of RAFT into smart synthesis platforms powered by artificial intelligence, enabling high-throughput and autonomous polymer discovery, and innovations in RAFT depolymerization that support sustainable plastic recycling. With RAFT increasingly accessible to diverse materials science domains, this review provides a forward-looking perspective on the evolving capabilities and future potential of RAFT polymerization.