Photoelectron spectral intensities of some first transition series elements were studied for metal cyanides containing inequivalent atoms. The spectra of low-spin ions coordinated via carbon to the cyanide ion, and of high-spin ions coordinated through nitrogen were separately obtained from manganese, iron, and cobalt cyanides. Metal 2p spectra obtained as sums of the appropriate spectra of low- and high-spin ions were nearly coincident with the spectra of the compounds containing inequivalent atoms. These results show that the intensity of the 2p electron for each atom must include the main peak and perhaps multiplet splitting effects, shake-up effects, and the inelastic scattering tail, and verify the non-interaction nature of the inequivalent atoms in these compounds