Ultrasoft X-ray emission spectra (USXES) and X-ray absorption near-edge structure (XANES) spectra with the use of synchrotron radiation in the range of P L2,3-edges were obtained for the first time for nanostructures with InP quantum dots grown on GaAs 〈100〉 substrates by vapor-phase epitaxy from metal–organic compounds. These spectra represent local partial density of states in the valence and conduction bands. The additional XANES peak is detected; its intensity depends on the number of monolayers forming quantum dots. Assumptions are made on the band-to-band origin of luminescence spectra in the studied nanostructures.