In this letter, the use of an ordered ultrathin ZnSe dipole layer to significantly modify the band discontinuity at the Si/Ge(111)-c(2×8)heterojunction is reported. Soft x-ray photoemission spectroscopy (SXPS) was utilized to monitor the evolution of the interface. The ZnSe intralayer increased the valence band offset by ∼0.57 eV, as compared to a negligible valence band offset for the Si/Ge(111) junction. This dramatic modification is interpreted in terms of the charge transfer at the interface. ©1998 American Institute of Physics.