The electronic structure of Co (100 Å)/Cu (50 Å) bilayer film on Si(100) has been investigated using valence band photoemission at 50 eV. The aim is to understand the Co/Cu interface and the nature of intermixing in Co and Cu layers. The valence band of Co/Cu interface shows three features at −0.3, −1.17 and −1.9 eV binding energy. The experimental observations are explained with the help of calculations based on projected augmented wave pseudopotential method using density functional theory. The origin of −0.3 eV feature is mainly due to the Co 3d minority spin states while the features at −1.17 and −1.9 eV are due to the formation of Co and Co–Cu mixed nanoclusters at the interface.