We report on the enhanced electromechanical, magnetic and magnetoelectric properties of Bi1−xCaxFe1−xTixO3 solid solutions. The crystal structure of the x≈0.25 compounds are close to the rhombohedral–orthorhombic phase boundary, and the solid solutions are characterized by increased electromechanical properties due to the polarization extension near the polar–nonpolar border. The homogenous weakly ferromagnetic state is established at x>0.15 doping. The chemical doping shifts the magnetic transition close to room temperature, thus enlarging the magnetic susceptibility of the compounds. The solid solutions at the morphotropic phase boundary exhibit a nearly twofold increase in piezoelectric response, whereas the magnetoelectric coupling shows five times enhancement in comparison with the parent bismuth ferrite.
► Bi1−xCaxFe1−xTixO3 solid solutions with composition near the morphotropic phase boundary. ► The structural softening increases the electromechanical properties of the compounds. ► The ME coupling is caused by an improving of the electric and magnetic subsystems.