Piezoelectric materials, which convert mechanical vibration energy into electric energy, are essential for vibration energy harvester. Nevertheless, the piezoelectric energy harvesting also encounters the bottleneck that piezoelectric materials generally produce only micro scale current due to its high impedance. In this work, the developed lead-free (Ba0.85Ca0.15)0.9985Sm0.001(Ti0.9Zr0.1)O3 (BCSm0.001TZ) piezoelectric ceramic possesses both high piezoelectric charge constant and low impedance, boosting its energy harvesting performance: an extremely high short-circuit current (60 µA) and large power density (2.1 µW/mm3) in a cantilever-type energy harvester, which is superior to those of other reported ones. Due to the giant current performance, the related charging speed of BCSm0.001TZ energy harvester possessed ~100% enhancement relative to the non-doped counterpart. Electrical property measurement and nanostructure observation revealed that the outstanding electromechanical properties as well as energy harvesting performances in BCSm0.001TZ ceramic benefits from a complex domain architecture and low concentration of defect, which is closely associated with the local structural heterogeneity induced by the rare-earth Sm doping. This work provides a new important paradigm for developing high-performance viable green energy materials and devices, especially for the fast recharging microelectronic storage devices in wireless sensor network.