The electronic and geometrical structure of A2FeMoO6 (A = Ca, Sr, Ba, Ba1/2Sr1/2) compounds has been investigated by means of x-ray absorption spectroscopy at the iron and molybdenum K-edges. The Mo-O distances extracted from the Mo K-edge EXAFS spectra are almost identical for all compounds while XANES spectra show small differences depending on the divalent metal. The XAS spectra at the Fe K-edge showed significant differences instead. Our analysis suggests an influence of the divalent A-metal in the electronic state of iron and molybdenum. Both the chemical shift at the iron K-edge and the interatomic Fe-O distances, closely correspond to Fe3+ for Sr2FeMoO6 and Ca2FeMoO6 while a mixed valence state (between +2 and +3) is deduced for the Ba sample. Accordingly, the Mo valency is higher for the barium sample.