New photosensitive alkoxyamines have been designed using molecular orbital calculations to improve the selective C-O versus N-O cleavage. The targeted light-sensitive alkoxyamine is synthesized in one step and its reactivity under UV has been investigated using both ESR and LFP. The ability of this alkoxyamine to control the photopolymerization of n-butyl acrylate is evidenced through a process called nitroxide-mediated photopolymerization NMP2. The selected alkoxyamine is finally used to prepare covalently bonded multilayered micropatterns. This original application highlights the high potential of this technique for some specific applications that require spatial control.