Composite insulating materials with enhanced dielectric permittivity, like silicone gel with barium titanate particles (BaTiO3) are promising candidates in the context of advanced field grading encapsulants for power electronic applications. The recent developments of field-assisted assembly techniques for particle structuration in polymeric matrix enable to obtain anisotropic material properties in the direction where it is the most suitable. This approach allows going beyond some composite intrinsic limitations and paves new ways to improve insulating materials to reach higher voltage performances at power system level. This paper aims to present the effect of dielectrophoretic electric field waveform and frequency on the anisotropic structuration of BaTiO3 particles in silicone gel and to report on the impact of these parameters on the chain formation.