Solid-state sintering method was used to prepare ceramic materials based on bismuth ferrite, i.e., (BiFeO3)1 − x –(BaTiO3) x and Bi1 − x Nd x FeO3 solid solutions and the Aurivillius Bi5Ti3FeO15 compound. The structure of the materials was examined using X-ray diffraction, and the Rietveld method was applied to phase analysis and structure refinement. Magnetoelectric coupling was registered in all the materials using dynamic lock-in technique. The highest value of magnetoelectric coupling coefficient α ME was obtained for the Bi5Ti3FeO15 compound (α ME ~ 10 mVcm−1 Oe−1). In the case of (BiFeO3)1 − x –(BaTiO3) x and Bi1 − x Nd x FeO3 solid solutions, the maximum α ME is of the order of 1 and 2.7 mVcm−1 Oe−1, respectively. The magnitude of magnetoelectric coupling is accompanied with structural transformation in the studied solid solutions. The relatively high magnetoelectric effect in the Aurivillius Bi5Ti3FeO15 compound is surprising, especially since the material is paramagnetic at room temperature. When the materials were subjected to a preliminary electrical poling, the magnitude of the magnetoelectric coupling increased 2–3 times.