A soft X-ray photoelectron spectroscopy with Zr Mζ radiation is used to investigate semiconductor surfaces. Zr Mζ photons of 151.4eV energy have good surface sensitivity, because Si2p photoelectron energy was about 50eV where the escape depth reaches minimum (0.5nm). The surface sensitivity was 10times higher than these in conventional techniques, and this result was in good agreement with that of theoretical calculation according to the difference of electron escape depth. Thanks to this high surface sensitivity, the Surface Core Level Shift (SCLS) was found to be -0.5eV in Si (100) 2×1 surface. We also used this technique to study the oxygen adsorbed surfaces layers at room temperature on Si (100) 2×1. The significant difference in photoelectron spectra was observed after annealing above 650°C.