The electronic structures of Co-based Heusler alloys with nonstoichiometric atomic compositions as well as those at the interface of semiconductor junctions are investigated using first principles band calculations. It is shown that the electronic structure of a Co-based Heusler alloy is half-metallic, even for nonstoichiometric but Co-rich compositions, whereas the half-metallicity is lost for Co-poor compositions. It is also shown that magnetic moments at the interface of Co2MnSi/ Si junctions are sensitive to the growth direction and interface structure of the junctions. Efficient spin-injection into Si can be achieved by using a (111)-oriented Co-rich Heusler alloy and controlling the layer-by-layer stacking sequence at the interface.