We use core level and valence band soft X-ray photoemission spectroscopy (SXPES) to investigate the electronic structure of new BiS2 layered superconductor LaO1-xFxBiS2. The core level spectra of doped samples show a new spectral feature on the lower binding energy side of the Bi 4 f main peak, which may be explained by core-hole screening with metallic states near the Fermi level (E-F). The experimental electronic structure and its x dependence (a higher binding energy shift of the valence band as well as appearance of new states near E-F having the dominant Bi 6p character) were found to be consistent with the predictions of band structure calculations in general. Noticeable deviation of the spectral shape of the states near EF from that of calculations might provide insight into interesting physical properties. This study provides the first experimental electronic structure of the new BiS2 layered superconductors.