Cyanoacrylates (CAs) are well-known fast-setting adhesives, which are sold as liquids in the presence of stabilizers. Rapid anionic polymerization on exposure to surface moisture is responsible for instant adhesion. The more difficult, but synthetically more useful radical polymerization is only possible under acidic conditions. Recommendations on the handling of CAs and the resulting polymers are provided herein. In this review article, after a general description of monomer and polymer properties, radical homo- and copolymerization studies are described, along with an overview of nanoparticle preparations. A summary of our recently reported radical polymerization of CAs, using reversible addition-fragmentation chain transfer (RAFT) polymerization, is provided.