In this paper, 0.94Bi0.5Na0.5TiO3–0.06BaTiO3 (BNBT6) lead-free piezoelectric ceramics have been prepared using the gelcasting technology. The dielectric and piezoelectric properties of these ceramics have been investigated. The specimens were sintered at 1100–1200 °C after grain-oriented under the pulsed strong magnetic field during the solidification of the green bodies. Compared with the BNBT6 samples without applying magnetic field, the ceramics textured by applying 5 T pulsed magnetic field has a coercive field with reduction of 400 V/mm, which makes the polarization process easier. Meanwhile, it is noted that the orientation degree increases with increasing sintering temperature, whereas the piezoelectric constant and electromechanical coupling coefficients are improved. If SrTiO3 seed grain is introduced, the orientation degree can reach 0.70 and the relative density of the sintered ceramics is up to 96%. The dielectric properties are anisotropic in directions vertical and parallel to the applied magnetic field. At around 180 °C, the dielectric constant in the direction vertical to the magnetic field is three times of that in the direction parallel to the magnetic field. And the dielectric loss in the direction vertical to the magnetic field is also higher than that in the direction parallel to the magnetic field.