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The band alignment of a (0001)CdS/CdTe heterojunction is in situ studied by synchrotron radiation photoemission spectroscopy (SRPES).The heterojunction is formed through stepwise deposition of a CdTe film on a wurtzite (0001)CdS single crystalline substrate via molecular beam epitaxy.CdS shows an upward band bending of 0.55 eV,the valence band offset △Ev is calculated to be 0.65 e V and the conduction band offset △ Ec is 0.31 eV.The interracial band alignment is sketched to display type-Ⅰ band alignment.