The investigation of valence band structure and electronic parameters of constituent element core levels of α-SrB(4)O(7) has been carried out with x-ray photoemission spectroscopy. Optical-quality crystal α-SrB(4)O(7) has been grown by the Czochralski method. Detailed photoemission spectra of the element core levels have been recorded from the powder sample under excitation by nonmonochromatic Al Kα radiation (1486.6 eV). The band structure of α-SrB(4)O(7) has been calculated by ab initio methods and compared to XPS measurements. It has been found that the band structure of α-SrB(4)O(7) is weakly dependent on the Sr-related states.