The valence band structures of a 35-nm-thick BaSi2 epitaxial film on Si(111) have been explored at room temperature by hard x-ray photoelectron spectroscopy (HAXPES). The experimentally obtained photoelectron spectrum is well reproduced by first-principles calculations based on the pseudopotential method. The top of the valence band consists mainly of Si 3s and 3p states in BaSi2, suggesting that the effective mass of holes is small in BaSi2. This is favorable from the viewpoint of solar cell applications. The observed spectrum shifted slightly to the lower energy side due to n-type conductivity of BaSi2. The valence band top was observed at about 0.8 eV below the Fermi level in the HAXPES spectrum.