We report on the use of an alkoxyamine (AA) for fabrication of functional micropatterns with complex structures by UV mask lithography. The living character of the polymer surface and the vertical spatial control of the repolymerization reaction from few tens of nanometers to few micrometers were demonstrated. The impact of the main parameters governing the controlled polymerization and the reinitiation process activated by light or heat was investigated. Micropatterning is shown to be a powerful method to investigate the physicochemical molecular phenomena. It is possible to control the polymer microstructure thickness from few tens of nanometers to few micrometers. In the last section, some applications are provided showing the potential of the AA for generating covalently bonded hydrophilic/hydrophobic micropatterns or luminescent surfaces. This demonstrates the high versatility and interest of this route.