Electronic structures of Fe overlayers on Cr(Fe/Cr) films, with an Fe coverage of $1-20{AA}$, have been investigated by using photoemission spectroscopy. Experimental results are compared with supercell band structure calculations for a system with monolayer (ML) Fe on each side of five layer Cr, Fe(1ML)/Cr(5ML)/Fe(1ML). The extracted Fe 3d partial spectral weight in Fe/Cr exhibits very interesting features for very thin Fe overlayers. First, a sharp emissionnear the Fermi energy is observed, which is expected to originate primarily from hybridization between Fe and Cr 3d electrons at the Fe/Cr interface, and partially from the Fe 3d surface states in the Fe overlayer. Second, other structures are observed at higher binding energies which resemble the Cr 3d valence bands, also suggesting large hybridization between Fe and Cr 3d states at the Fe/Cr interface. These conjectures are confirmed by band structure calculations for Fe(1ML)/Cr(5ML)/Fe(1ML).