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Using low electron energy‐loss spectroscopy, we showed previously the existence, on monocrystalline Al(111), of an electronic transition involving surface states. This work is extended to another crystallographic orientation Al(100). Main results show that the transition energy depends both on the surface orientation and on the primary energy. Its dispersion has been followed for primary energies ranging from 10 to 100 eV. In order to better characterize the location of these states in the surface band structure E(k‖), experiments have been combined with UV inverse photoemission spectroscopy, which gives direct access to the unoccupied states above the Fermi level. The results are discussed in the frame of surface band calculations.