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Morphotropic phased boundary (MPB) existent Bi 0.5 (K 0.2 Na 0.8) 0.5 TiO 3 :xwt%MnO 2 (BKNT:xMn) ceramic system is fabricated to investigate the ferroelectric and piezoelectric properties. All the ceramic samples have maintained the tetragonal (P4mm)-rhombohedral (R3c) structural duality due to MPB regional investigation of BKNT. The addition of MnO 2 in BKNT has improved the multifunctional properties of the material at x ​= ​0.15. BKNT:0.15Mn ceramic has shown the maximum density of 6.98 ​g/cm3, remnant polarization (P r) ​∼ ​32.5 ​μC/cm2, high impedance of ∼108 ​Ω, d 33 of 206 ​pC/N, which are much improved properties than pure single phase BKNT and Bi 0.5 K 0.5 TiO 3 ceramics. The dependence of dielectric constant (ε r) on temperature suggests the relaxor behavior and the high Curie temperature (T C) ​∼ ​410 ​°C for BKNT:0.15Mn ceramic, higher than the T C ​∼ ​360 ​°C of pure BKNT ceramic. The poled ceramics have maintained the stable piezoelectric properties till 300 ​°C. The introduction of multivalence Mn has improved the multifunctional properties of the material significantly, making it a strong candidate to be utilized in actuators and sensors. [Display omitted] • Morphotropic phased boundary (MPB) existent Bi 0.5 (K 0.2 Na 0.8) 0.5 TiO 3 :xwt%MnO 2 (BKNT:xMn) ceramic system is fabricated. • All the ceramic samples have maintained the tetragonal (P4mm)-rhombohedral (R3c) structural duality due to MPB regional investigation of BKNT even after the addition of xwt%MnO 2. • BKNT:0.15Mn ceramic has shown the maximum density of 6.98 ​g/cm3, and remnant Polarization of P r ∼32.5 ​μC/cm2. • BKNT:0.15Mn has shown high impedance of ∼108 ​Ω and d 33 of 206 ​pC/N, which are much improved from the properties of pure Bi 0.5 K 0.5 TiO 3 ceramic. • The relaxor behavior and the high Curie temperature (T C) of ∼410 ​°C has been observed for BKNT:0.15Mn ceramics. [ABSTRACT FROM AUTHOR]