Two series of iron-containing solid solutions Bi2Mg1-xFexNb2O9+δ and Bi2MgNb2-2xFe2xO9-δ of pyrochlore structure were obtained by the traditional solid phase synthesis method. The electronic state and character of exchange interactions of iron atoms in solid solutions were investigated by methods of magnetic dilution and NEXAFS-spectroscopy. According to X-ray spectroscopy and magnetic susceptibility data, iron(III) atoms are distributed mainly in octahedral positions of niobium(V) and in a dominant amount are in the charge state of Fe(III) in the form of monomers and exchange-bonded clusters mainly with antiferromagnetic type of exchange. Differences in magnetic behavior of iron-containing solid solutions of both series have been revealed. Antiferromagnetic and ferromagnetic exchange can be realized between iron atoms, which, with increasing concentration of paramagnetic atoms and averaging structure distortions, becomes less significant. The parameters of exchange interactions in clusters and distribution of iron paramagnetic atoms depending on the concentration of solid solutions have been calculated.