The electronic and structural properties of LiB 3 O 5 (LBO) surfaces have been studied by X-ray photoemission spectroscopy (XPS) and reflectance high-energy electron diffraction (RHEED). The as-grown (110) crystal face and mechanically polished (001) surfaces have been investigated comparatively. Electronic structure of LBO has been determined on as-grown (110) crystal face previously cleaned by chemical etching with RHEED control. The correlation of valence band structure and measured binding energies with earlier reported results has been discussed. Core-level spectroscopy reveals strong enriching of mechanically polished LBO surface with carbon, when nanodiamond powder is used as an abrasive. So high carbon level as C:B=0.7 has been observed at the surface while the ratio Li:B:O remains according to LBO chemical composition. The association of LBO Kikuchi-lines with strong background has been shown by RHEED analysis of the surface. Thus, the polished LBO surface constitutes a high structure quality LBO with the inclusions of some amorphous carbon compound.