In the present study, lead-free piezoelectric (1-x)[(Bi 0.96 La 0.04 ) 0.5 Na 0.5 TiO 3 ]-(x)[Ba 0.90 Ca 0.10 TiO 3 ] ceramics with x ≤ 0.20 have been prepared at optimum temperature (950°C–1050 °C) by employing semi-wet technique. The effect of Ba 0.90 Ca 0.10 TiO 3 (BCT) content on the phase formation, surface morphology, dielectric and piezoelectric properties is systematically investigated and characterized by X-ray diffraction (XRD), Raman Spectroscopy, Field emission Scanning electron micrographs (FE-SEM), Impedance analyzer. XRD analysis shows phase transformation from rhombhohedral to tetragonal with the addition of BCT and the average grain size decreases with BCT content, x. Temperature dependent dielectric behavior exhibits two phase transitions, i.e. depolarization temperature; T d and phase transition temperature; T m . The phase transitions; T m tends to diffuse with increasing x and exhibited a broad frequency dependent maximum upto x ≤ 12. Optimum piezoelectric and dielectric properties (i.e., d 33 = 165 pC/N, k p = 39%, k t = 47% and k 33 = 57%, ε r = 1585, tan δ = 0.07) in the studied system have been obtained. [ABSTRACT FROM AUTHOR]