Chemical reaction with diazonium molecules has revealed to be a powerful method for the surface chemical modification of graphite, carbon nanotubes and recently also of graphene. Graphene electronic structure modification using diazonium molecules is strongly influenced by graphene growth and by the supporting materials. Here, carrying on a detailed study of core levels and valence band photoemission measurements, we are able to reconstruct the interface chemistry of trimethoxybenzenediazonium-based molecules electrochemically grafted on graphene on copper. The band energy alignment at the molecule-graphene interface has been traced revealing the energy position of the HOMO band with respect to the Fermi level. © 2020, The Author(s).