Taking the average bond energy Em as reference level, and empitical pseudopotential scheme is employed to calculate the band alignment(including valence band, conduction band, and band gap) of three semiconductor heterojunctions:GaAs/Ge,AlAs/GaAs and AlAs/Ge and the complete and more accurate calculation results are obtained. In our calculation, the valence -band offset values ΔＥｖ of the above three heterojunctions are ０.５７，０.５０ and １.０７ｅＶ,respectively．