Abstract New solid solution of Na 0.5 Bi 0.5 TiO 3 with BaFeO 3− δ materials were fabricated by sol–gel method. Analysis of X-ray diffraction patterns indicated that BaFeO 3− δ materials existed as a well solid solution and resulted in distortion the structure of host Na 0.5 Bi 0.5 TiO 3 materials. The randomly incorporated Fe and Ba cations in the host Na 0.5 Bi 0.5 TiO 3 crystal decreased the optical band gap from 3.11 to 2.48 eV, and induced the room-temperature ferromagnetism. Our density-functional theory calculations further suggested that both Ba for Bi/Na-site and Fe dopant, regardless of the substitutional sites, in Na 0.5 Bi 0.5 TiO 3 lead to the induced magnetism, which is illustrated in terms of the exchange splitting between spin subbands through the crystal field theory and Jahn–Teller distortion effects. Our work proposes a simple method for fabricating lead-free ferroelectric materials with ferromagnetism property for multifunctional applications in smart electronic devices.