The current chapter highlights the latest developments in the fields of enhanced spin capturing polymerization (ESCP), in situ nitroxide mediated radical polymerization (in situ NMP) as well as nitroxide mediated photo-polymerization (NMP2), critically embedded into the latest developments in the wider field of reversible deactivation polymerization. Specific examples for each area are provided, noting the specific advantages and disadvantages of each technique, spanning the fields of block and star copolymer design to spatially resolved gradient surfaces.