We have grown pseudomorphic single crystal Si1-x-yGexCy layers on Si(100) substrates by Rapid Thermal Chemical Vapor Deposition with up to 2.5 percent substitutional carbon. Capacitance-voltage as well as admittance spectroscopy measurements have been used to study the effect of carbon on the valence band offset of compressively strained Si1-x-yGexCy/(100)Si heterojunctions. The valence band offset of Si1-x-yGexCy/Si decreased by 25-30 meV, indicating that all the change in bandgap of Si1-xGex as carbon was added is accommodated in the valence band.