Soft X-ray absorption (XAS) and emission (XES) spectroscopies were applied to determine valence states of manganese ions in nanostructured powder of half-doped (Formula presented.) manganite obtained by milling in a ball mill. XAS spectra were measured both in surface-sensitivity total electron-yield and in bulk-sensitivity total fluorescence-yield modes. O K(Formula presented.) XES and O 1s XAS spectra characterized the occupied and unoccupied partial O 2p densities of states are compared with band-structure calculations made using the TB-LMTO-ASA codes. Experimental Mn 2p, Ca 2p, and La 3(Formula presented.) XAS spectra are compared with results of crystal field atomic multiplet calculations. For the nanostructured system of (Formula presented.), concentrations of Mn(Formula presented.) ions are found to be increased with increasing the time of milling.