Nanostructured Pb0.98La0.02(Ni1/3Sb2/3)0.05[(Zr0.52Ti0.48)0.995]0.95O3 ferroelectric ceramic has been synthesized for the first time by columbite precursor method followed by mechanical activation (MA) from 5 to 40 h of dry oxide powders using high‐energy ball mill, thereby evading the calcination stage. Progressive perovskite phase formation and transformation by MA were investigated from X‐ray diffraction (XRD) analysis, indicating the noticeable presence of perovskite phase after 10 h of milling. Particle morphology of the powder was analyzed by HRTEM and correlated with activation time. Furthermore, the effect of activation time on microstructure and piezoelectric properties of the samples sintered at 1220°C were investigated. Compact microstructure, composition at morphotropic phase boundary, optimum tetragonality, and crystallinity obtained for the sintered samples resulted in best possible piezoelectric charge coefficient, d33 (449 × 10−12 C/N), piezoelectric voltage coefficient, g33 (32 × 10−3 m.V/N), and figure of merit for power harvesting, FoMPH (14.4 × 10−12 m‐V.C/N2), for 10 h of activation. The experimental data on output voltage in response to simulated random vibrations of aerospace vehicles measured in frequency band of 20–2000 Hz were also optimum for 10 h activation, which confirm the suitability of this composition for power‐harvesting applications.