In this work, we studied the effect of heterovalent Ca, Sr, Pb, and Ba substitution on the crystal structure, dielectric, local ferroelectric, and magnetic properties of the BiFeO3 multiferroic perovskite. Ceramic solid solutions with the general formula Bi0.7A0.3FeO3 (A is a doping element) were prepared and characterized by x-ray diffraction, dielectric, piezoresponse force microscopy (PFM), and magnetic measurements. It is shown that the crystal structure of the compounds is described within the space group R3c, permitting the spontaneous polarization, whose existence was confirmed by the PFM data. Magnetic properties of the solid solutions are determined by the ionic radius of the substituting element. Experimental results suggest that the increase in the radius of the A-site ion leads to the effective suppression of the spiral spin structure of BiFeO3, resulting in the appearance of net magnetization.