Selective Laser Sintering (SLS), as an important 3D printing technology, enables to fabricate parts with any complicated shapes that can’t be achieved by traditional polymer processing technology, and is widely used in aerospace, defense equipment, medical apparatus, automobiles and other high-tech fields. At present, the SLS processing faces the bottlenecks in the limited range of polymer materials, lacking function and the high cost in the production of powder. In this work, spherical PA11/BaTiO3 piezoelectric composite powder suitable for SLS processing was prepared at a large-scale by innovatively combining the solid state shear milling (S3M) and spheroidization techniques. The results indicated that the S3M technique could efficiently realize better dispersion of BaTiO3 particles in the PA11 matrix and improve their interfacial compatibilities. The tetragonal structure of the BaTiO3 particles was not destroyed by S3M treatment. Moreover, the sintering window and viscosity of the S3M treated PA11/BaTiO3 composite were increased and decreased, respectively, endowing the composites with better processability. The spherical PA11/BaTiO3 piezoelectric composite powders with uniform structure were obtained by our patented technique for spheroidization of polymer-based micro/nano functional composite powder. The spheroidized powder exhibited higher initial flow property and improved stability, consolidation, permeability and fluidization properties as compared with the raw powder. Finally, the porous PA11/BaTiO3 piezoelectric parts with complex shape and excellent mechanical-to-electrical conversion property that can’t be achieved by traditional polymer processing, were fabricated for the first time by macro/micro structure design and SLS processing. The generated output was sufficient to light up twelve commercial light-emitting diodes (LED) bulbs instantaneously. This work was supported by the National Natural Science Foundation of China (51433006).