Click chemistry is widely used in materials and surface science for its high efficiency, ease of use and high yields. Azide-terminated SAMs have been prepared successfully by using three different deposition methods (post-functionalization and direct grafting by immersion as well as spin coating). Strikingly, our study shows that the reactivity of the azido group on the surface with the alkyne in solution is not trivial and seems to be closely related to the orientation of the azide. Indeed, more the azide is vertically oriented more it is accessible and reactive. The orientation of azido dipoles at the surface depends strongly on the method used to prepare the monolayer. The post-functionalization method allows to have a homogeneous population of the azide groups on the surface with a better vertical orientation than that obtained using direct grafting by immersion or spin coating processes. Whatever the type of azide-terminated SAMs, the reactivity of the accessible vertical azido groups is complete. This study clearly demonstrates that it is possible to control the amount of reactive azides and, consequently, the amount of molecules immobilized on the surface after the click reaction by choosing the deposition method.