The role of Pr6O11 addition on the structure, microstructure, electrical, and electromechanical properties of lead‐free (Ba0.85Ca0.15)(Ti0.90Zr0.10)O3 piezoelectric ceramics has been systemically investigated. Addition of praseodymium (Pr) results in improved ferroelectric and piezoelectric properties. XRD analysis revealed the co‐existence of rhombohedral (R) and tetragonal (T) phases at room temperature. High remanent polarization values (2Pr ~17 μC/cm2) and loop squareness of nearly 0.87 were obtained for the BCZT‐0.04 wt%Pr ceramic, along with high piezoelectric coefficient (d33 = 435 pC/N) and transduction coefficient [(d33·g33) = 11589 × 10−15 m2/N]. Results are correlated with the crystal structure and microstructure that significantly influence the ferroelectric and piezoelectric properties near the R–T phase transition point. This material seems to be especially suitable for energy harvesting applications, exhibiting outstanding figure of merit.