The atomic and electronic structure of the graphene/Al/Ni(111) system is studied via combination of LEED and spectroscopic methods (X-ray absorption, core-level and valence-band photoelectron spectroscopy), respectively. These data demonstrating the (2 x 2) overstructure and the decoupling of the graphene layer from the substrate (with respect to graphene/Ni(111)) are in very good agreement with DFT calculations supporting nearly free-standing state of graphene in this system (with small n-doping). The perspectives of application of Al-based intercalation-like systems are discussed. (C) 2012 Elsevier B. V. All rights reserved.