The polymerization and chemistry of activated acrylates have been elaborated in recent years to provide a uniquely versatile method of polymer synthesis. The new method is simple, generally applicable, and is ideally suitable for the synthesis of specialty polymers of interest in the emerging technologies in chemistry, engineering, biotechnology and medicine. This article discusses the polymerization and copolymerization of activated acrylates by solution and suspension techniques, and reviews polymer properties such as comonomer distribution, molecular weights, ¹³C-NMR spectra and gel morphology. The use of copolymers of activated acrylates for the synthesis of a variety of specialty polymers, including amphiphilic gels, graft copolymers, and side chain reactive and liquid crystalline polymers is outlined. Potential applications of these polymers are also highlighted, and the versatility of active ester synthesis as a new dimension of creativity in macromolecular chemistry is emphasized.