Valence-band electronic density of states of Yb2.75C60 thin films was measured by the ultraviolet photoemission spectrum technique. The phase-pure Yb2.75C60 sample was characterized by the C 1s XPS measurements. The result indicates Yb2.75C60 has no Fermi edge and thus is semiconductor. The hybridization between 6s state of Yb and the LUMO band of C60 cannot be considered to be negligible. Some Yb 6s electrons occupy the Yb-C60 covalent band in Yb2.75C60.