Holmium-doped BaTiO3 with composition Ba0.97Ho0.03TiO3 was prepared by sol-gel combustion method. A molar ratio of citrate/nitrate (CA/NO3− = 1.3) was used to prepare nanopowders of (Ba,Ho)TiO3. The structure and microstructure of (Ba,Ho)TiO3 powders and ceramics were investigated. The ceramics exhibit a dielectric constant of about 4400 and dielectric loss (tan δ = 0.267) at 10 Hz, and at the Curie temperature (Tc = 132 °C). The remanent polarization and the coercive field of Ba0.97Ho0.03TiO3 ceramics, at 1 kHz, were Pr = 6 μC/cm2 and EC = 0.75 kV/cm. The dielectric and ferroelectric behavior of the holmium-doped BaTiO3 is influenced by the amphoteric character of Ho3+ ions.