The design of piezoelectric roads is one of the future directions of smart roads. In order to ensure the environmentally friendly and long-lasting use of piezoelectric road materials, lead-free piezoelectric ceramics (barium titanate), polymer piezoelectric materials (polyvinylidene fluoride), and conductive particles (conductive carbon black and graphene) were used to prepare composite piezoelectric materials. The electrical performance was studied by the conductivity, dielectric properties, and piezoelectric properties of the composite materials. Then, the mechanical properties of the composite material were investigated by load compression tests. Finally, the microstructure of the composite materials was studied. The results showed that as the amount of conductive particles increased, the electrical performance was improved. However, further addition of conductive particles led to a decline in the electrical performance. The addition of conductive particles had a minimal effect on the mechanical properties of composite materials. The composite material met road use requirements. The overall structure of the composite materials was compact, with a clear wrapping effect of the polymer, and good interface compatibility. The addition of conductive carbon black and graphene had no significant impact on the structure of the composite materials.