Novel perovskite-type (1 − x)BaTiO₃–xBiYbO₃ solid solutions with x = 0.00–0.20 were synthesized using conventional solid-state reaction methods. A systematic structural change from ferroelectric tetragonal to pseudo-cubic phase was observed at about x = 0.050–0.051 at room temperature. Dielectric measurements revealed a gradual change from normal ferroelectric behavior to highly diffusive and dispersive relaxor-like characteristics, wherein the phase transition temperature shifted to a higher temperature with increasing frequency. With an increase in the BiYbO₃ content, the nonlinearity of the (1 − x)BaTiO₃–xBiYbO₃ ceramic was weakened obviously. The bulk ceramics were characterized by high polarization maxima and low remnant polarization, which exhibit slim P–E hysteresis loops. The results demonstrate that the (1 − x)BaTiO₃–xBiYbO₃ ceramics are promising lead-free relaxor materials for energy storage applications.