Structurally diverse imidazole derivatives were synthesized by a visible-light/[Ru(bpy)(3)][(PF6)(2)]-mediated coupling of vinyl azides and secondary amines in flow microreactors. This operationally simple and atom-economical protocol allows the formation of three new C-N bonds through the functionalization of sp(3) C-H bonds adjacent to the secondary nitrogen atom. In order to get mechanistic insight of the coupling reaction, several control experiments were carried out and discussed.