To build piezoceramics with high transduction coefficient (d33 × g33) is the key to improve the power generation capability of piezoelectric energy harvester. Here, a new targeted doping strategy has been proposed to significantly increase the energy density of piezoceramics. Taking the modification of 0.2Pb(Zn1/3Nb2/3)O3‐0.8Pb(Zr0.5Ti0.5)O3 (PZN‐PZT) as an example, dual functions can be achieved by introducing appropriate amount of target‐doped (Zn0.1Ni0.9)TiO3 (ZTN9) based on its pyrolysis characteristics. On the one hand, Ni2+ ions enter the perovskite matrix to replace Zn2+ ions to form equivalent doping; on the other hand, it induces the formation of 0‐3 ZnO/perovskite composite structure, and both of which promote the large increase in d33 × g33 due to the changes in the domain configuration are more conducive to the ferro‐/piezoelectricity. In all compositions, 0.67 mol% ZTN9 added specimen has a maximum value (12 433 × 10−15 m2/N) of the d33 × g33. The cantilever piezoelectric energy harvester fabricated with this material generates up to 4.50 μW/mm3 of power density at 1 g acceleration, which is capable of quickly charging a 47 μF electrolytic capacitor and then lit 135 parallel‐connected commercial blue light‐emitting diodes (LEDs), showing its important application in implementing self‐powered microsensors.