Two series of Bi2Mg1-xCoxNb2O9 and Bi2MgNb2-2xCo2xO9-δ preparations with pyrochlore structure were synthesized using solid phase method. It was found that solid solutions are formed in Bi2MgNb2-2xCo2xO9-δ series, foreign phases of MgNb2O6 and Bi5Nb3O15 are fixed in Bi2Mg1-xCoxNb2O9 samples, no impurity cobalt-containing phases were detected. The method of magnetic susceptibility and NEXAFS-spectroscopy investigated the electronic state and character of exchange interactions of cobalt atoms in solid solutions with the pyrochlore structure. According to X-ray spectroscopy and magnetic susceptibility of cobalt atoms in solid solutions in a dominant amount are in the charge state of Co(II) in the form of monomers and exchange-bound clusters mainly with antiferromagnetic type of exchange. Ceramics Co-doping of multicomponent bismuth niobate pyrochlore has at room temperature a high dielectric permeability of 84 and small dielectric losses of 0.001. The energy of activation of conductivity is equal to 0.75–1.03 eV. This type of ceramics with excellent dielectric properties can potentially be used as multilayer ceramic capacitors.