Currently available low-dimensional piezoelectric materials show a low piezoelectric coefficient d33 of merely 100 pm V-1 with Pb(Zr, Ti)O3-based materials at the high end. Here, we report very large piezoelectricity in Ba(Ti0.80Zr0.20)O 3-0.5(Ba0.70Ca0.30)TiO3 (BTZ-0.5BCT) lead-free nanostructures sintered as thin films (d33 = 140 pm V -1) and nanofibers (d33 = 180 pm V-1). The influences of lateral size, geometry, and the clamping effect on the piezoelectric performance were investigated for both thin films and nanofibers. Combining a high piezoelectric coefficient with environmental benefits, the BTZ-0.5BCT nanostructures provide the superior functions sought for highly efficient piezoelectric devices and electromechanical systems. © 2014 AIP Publishing LLC.