Decoupling of the graphene layer from the ferromagnetic substrate via intercalation of sp metal has recently been proposed as an effective way to realize a single-layer graphene-based spin-filter. Here, the structural and electronic properties of the prototype system, graphene/Al/Ni(111), are investigated via a combination of electron diffraction and spectroscopic methods. These studies are accompanied by state-of-the-art electronic structure calculations. The properties of this prospective Al-intercalation-like system and its possible implementations in future graphene-based devices are discussed.