The crystal structure, microstructural evolution, and ferroelectric and magnetic properties of BiFeO3 (BFO) ceramic materials, widely known as room temperature multiferroic materials, were investigated with various contents of Ba(Cu1/3Nb2/3)O3 (BCN). The ceramics were synthesized through the solid state reaction and pressureless sintering in air. By adding tetragonal structured BCN phase to the rhombohedral structured BFO phase, a solid solution was formed. The rhombohedral crystal structure and lattice parameter, densification behavior, and microstructure of BFO were noticeably changed upon the addition of BCB. The electrical properties of BFO were slightly enhanced by the addition of BCN. However, the magnetic properties of BFO which is the most critical issue in BFO multiferroics were drastically changed and the 20 mol% BCN added BFO ceramics showed extremely enhanced magnetization characteristics compared to the other BFO–BCN ceramics. It is expected that BFO–BCN ceramics with this composition could be one of the most promising multiferroic materials for future multiferroic applications