The structural, electrical, luminescent, and magnetic properties of Eu3+-doped Ba0.77Ca0.23 (BCT23:Eu) ceramics were investigated in this paper. Three different incorporation mechanisms of were realized in BCT23 by considering different charge compensation mechanisms: (i) Ca site substitutes with Ca vacancy compensation; (ii) Ti site substitution with O vacancy compensation; (iii) simultaneous substitution at both Ca and Ti sites with self-compensation. Besides the evident ferroelectric proper the BCT23:Eu ceramics showed the photoluminescence and paramagnetic properties, implying that can be considered as the multifunctional materials. Both the electric and luminescent properties were sensitive to the Eu doping concentrations and positions, due to the variations of the microstructures different charge compensation mechanisms. (C) 2009 Elsevier B.V. All rights reserved