There are presented core-level 3s X-ray photoelectron spectra of some 3d oxides. The possibility to extract additional information on intra- and interatomic exchange effects from 3s X-ray photoelectron spectra is demonstrated. The results pointed to the possibility of using X-ray photoelectron 3s spectra for estimation of local spin magnetic moments localized on 3d elements in manganese and iron oxides. We have found that for doped manganites, the Mn formal valency from 3+ to 3.3+ is not accompanied by any decrease in the Mn 3s splitting. This fact can be explained by the holes in the O 2p states (d4L ground-state configuration). For Cu, Ni, and Co oxides, the charge-transfer effect dominates the multiplet effect in the 3s spectra which allows to estimate the occupancy of 3d states.