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Magnetic susceptibility, microstructure and EPR of cobalt-containing solid solutions with layered perovskite-like structure Bi5Nb3−3xCo3xO15−δ have been studied. Solid solutions of Bi5Nb3−3xCo3xO15−δ (x60.005) can be crystallized in tetragonal syngony (sp. gr. P4/mmm), as cobalt content increases, monoclinic distortion of the unit cell emerges at 0.005 &lt; x 6 0.04 (sp. gr. P2/m). The formation of exchange-bound aggregates of Сo(III) and Co(II) atoms predominantly with antiferromagnetic exchange types has been found in the solid solutions. EPR indirectly confirms that cobalt ions are in octahedral positions of substitution of Nb(V) ions

Magnetic Susceptibility and EPR Study of Bi₅Nb₃−₃ₓCo₃ₓO₁₅−δ