The chemical bonding states of boron (B) in shallow P+/N junctions on Si substrates were studied by soft x-ray photoelectron spectroscopy (SXPES). This study revealed three chemical bonding states of B embedded in bulk Si. The concentration profiles of B were successfully determined by combining SXPES with step-by-step etching of Si substrates. The concentration profiles of B thus determined were in good agreement with those determined by secondary ion mass spectroscopy. The concentration profiles of holes were also determined by combining Hall measurements with the step-by-step etching of Si substrates. The concentration profiles of B having the lowest binding energy were found to agree well with the concentration profiles of holes. Therefore, B with the lowest binding energy can be assigned as activated B and those having the middle and highest binding energies can be attributed to deactivated B having chemical bonding states different from that of activated B.