Unfilled tungsten bronze ceramics with a composition of Ba4SmFe0.5Nb9.5O30 were prepared by the conventional solid-state sintering method. The phase, microstructure, dielectric and ferroelectric properties were studied. Room temperature XRD results indicated that the ceramic occurs in the tetragonal space group P4bm phase with cell parameters of a=b=12.4712(2)Å and c=3.9430(2)Å. The temperature-dependent dielectric properties, XRD data and Raman spectra data indicated that BSFN ceramics exhibit no phase changes from 35°C to 450°C. Fitting of a Vogel-Fulcher relationship with an activated energy Ea of 0.11eV indicates an unambiguous dielectric relaxor state near room temperature. Furthermore, the BSFN ceramics exhibited residual polarization and coercive field of 3.45µC/cm2 and 24.65kV/cm, respectively.