3D printed piezoelectric devices, due to their sufficient multidimensional deformation and excellent piezoelectric properties, are one of the most promising research directions. However, the lack of high loaded piezoelectric composites is the key bottleneck restricting the enhancement of the piezoelectric output. In this work, we successfully prepared a novel high loaded polyvinylidene fluoride (PVDF)/barium titanate (BaTiO₃) piezoelectric composite suitable for selective laser sintering (SLS) 3D printing via solid state shear milling (S³M) technology. The 50 wt% BaTiO₃ filling made the most outstanding contribution to the piezoelectric properties of the composites. The 3D printed cymbal parts with a stress amplification effect exhibited outstanding piezoelectric conversion efficiency and responsiveness, whose open circuit voltage and short circuit current could reach 20 V and 1.1 μA, respectively. This work not only contributed a new high loaded piezoelectric composite for SLS processing, but also provided a novel piezoelectric performance enhancement strategy by the construction of 3D structure.