We report an investigation into the surface electronic structure of Pb/Cu(100) in the submonolayer coverage range. A prominent surface band is detected in the whole coverage range analysed. The band is gradually filled as Pb coverage increases. For a Pb coverage of 0.375 ML, corresponding to the c(4 × 4) phase, a strong c(4 × 4) folding of this state is observed in the valence band. The origin of these results and the nature of the surface electronic structure of Pb/Cu(100)- c(4 × 4) are discussed.