A sustained effort to develop and commercialize a practical radical addition route to amine functional polymers (AFPs) resulted, after almost 20 years, in the successful completion of a world scale monomer plant to produce N‐vinylformamide (NVF). NVF is readily polymerized and its polymers are easily hydrolyzed to reactive and atom economical polyvinylamine (PVAm) or its salts. This highlight touches on work by many companies, but focuses on efforts at Air Products and Chemicals, tracing the origins, rational, challenges, technical and commercial advances, and failures. Practical routes to new AFPs, copolymers, and derivatives across the entire molecular weight range (MW < 103 to >106) were achieved. NVF offers access to multiple water soluble, water dispersible, and nonwater soluble polymer markets, including papermaking additives and coatings, water treatment polymers, enhanced oil recovery polymers, radiation cure monomers, stabilizers, dispersing agents, surfactants, and crosslinkers. Lessons learned along the road to commercializing major new chemical technologies are also highlighted. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2257–2283, 2010