X-ray absorption spectra at the Co L-2,L-3-edges were analyzed by means of ligand field multiplet calculations in different states of three photomagnetic CoFe Prussian blue analogues of chemical formula Cs2Co4[Fe(CN)(6)](3.3)center dot 11H(2)O, Rb2Co4[Fe(CN)(6)](3,3)center dot 11H(2)O and Na2Co4[Fe(CN)(6)](3.3)center dot 11H(2)O. These simulations of the experimental spectra allowed the quantification of the crystal field parameter (10Dq). This determination led us (i) to evidence different behaviors of the Co-III(LS) and Co-II(HS) ions in the three-dimensional structure related to their electronic configurations, (ii) to propose an approach based on the electronic density distribution along the Co-NC-Fe linkage to account for the energy position of the states implied in the switching properties of the compounds, and (iii) to explain the different photomagnetic properties observed as a function of the size of the inserted alkali cation by competing interactions between the cyanide ion and the transition metal ions within the CoFe cyanide bimetallic network on the one hand and the cyanide ion and the alkali metal ions on the other hand.