This chapter traces the early history of nitroxide-mediated polymerization (NMP) during the first ~15 years. It begins with a short prehistory of observations, made during studies on defining initiation mechanisms using nitroxide radical trapping that can be seen to have inspired the initial experiments. The main part of the chapter is devoted to an account of the discovery of NMP in the early 1980s and research carried out in the period through to 1993, which saw most aspects of the polymerization mechanism defined and the process exploited at CSIRO mainly in the synthesis of acrylic block copolymers. We also provide a brief summary of developments in both the patent and open literature during the period 1993-2000 when the process came to the attention of the wider polymer community mainly for the controlled radical polymerization of styrenics. The end of this period saw the discovery of nitroxides such as SG1 and TIPNO, which provided improved utility and versatility to NMP.