The electronic structure and magnetic properties of the Fe(001) surface with Al overlayers, vice versa, are studied by means of ab initio band structure calculations using the LSW method. An Fe–Al(001) multilayer system is calculated for comparison. The calculations show that Al reduces the magnetic moments of the interface iron. The Al interface layer has a small negative magnetic moment. The interaction between the interface Al and Fe layers, and the intra-atomic exchange splitting are discussed.