Electronic structure and chemical state of high-Tc superconductor (La1-xSrx)2CuO4-δ (x=0.075 and δ≦0.04) were studied by photoelectron spectroscopy. Resonant photoemission with synchrotron radiation snowed that the copper atom in the La–Sr–Cu–0 system is mostly divalent. The experimental results were compared with the band calculations performed for La2CuO4.