Controlled radical polymerization has become one of the most indispensible tools for polymer chemists. The living character of this type of polymerization provides an ability to produce polymers with controlled molecular weight and narrow molecular weight distribution and to extend chains with different monomers to obtain multi-block copolymers. Nitroxide-mediated radical polymerization (NMP) is one of these controlled radical polymerizations, and stands out due to its simplicity: the polymerization is thermally initiated in the absence of an external radical source or a metal catalyst.