Free-radical polymerization processes play a dominant role in the industrial preparation of a wide variety of polymeric materials. This is due to various factors, such as mild reaction conditions, compatibility with a range of monomer units, and so on. However, the disadvantages of free-radical polymerizations are that the polymers obtained are frequently polydisperse and there is little, if any, control over architecture and structure. Recently, a new approach to free-radical polymerizations, in which a stable counter free radical is present, has been developed in an effort to overcome many of the shortcomings of normal free-radical polymerizations. The presence of the counter free radical mediates the reactivity of the growing radical chain end and leads to a living polymerization. It has been shown that this living nature permits a degree of control over macromolecular architecture and structure that rivals living anionic or cationic processes. The fundamentals behind the living free-radical polymerization process are reviewed, with special emphasis given to the potential of this novel procedure for control of architecture and structure.