Discontinuities in the energies of the conduction and valence bands at semiconductor heterojunctions are important parameters for device design. We describe experiments using X-ray photoelectron spectroscopy with measurements of valence-band energies with respect to core-levels of metastable, coherently strained Si 1 - x Ge, alloy layers and of thick Ge 1 - y C y alloy layers. For strained Si 1 - x Ge x alloys on Si, we have found that the valence band offset increased with the Ge fraction x with most of the offset in the valence band. We obtained a valence band offset of 0.22 eV for x = 0.23, in good agreement with theoretical calculations. For Ge 1 - y C y alloys, we found very little shift in the valence band energies with the C fraction y. Since the optical bandgap of GeC increased with the C fraction y, most of the offset for Ge 1 - y C y /Ge heterojunction was in the conduction band. Based on the measurements of the energy band offsets of Si 1 - x Ge x /Si, we infer that the major portion of bandgap discontinuity of Ge 1 - y C y on Si is in the valence band. Ge 1 - y C y alloys are new metastable materials that open up a new region for group IV heterostructures.