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In the present era of advanced technology, the surge for suitable multifunctional materials capable of operating above 300 °C has increased for the utilization of high-temperature piezoelectric devices. For this purpose, a pseudo-tetragonal phased CaBi₄Ti_3.98 (Nb_0.5Fe_0.5)_0.02O₁₅:<i>x</i>wt%MnO₂ (CBTNF:<i>x</i>Mn), with <i>x</i> = 0–0.20, ceramic system has been engineered for the investigation of structural, ferroelectric, dielectric and high-temperature-dependent piezoelectric properties. XRD analysis confirms that low-content Mn-ion insertion at the lattice sites of CBTNF does not distort the pseudo-tetragonal phase lattice of CBTNF:<i>x</i>Mn ceramics, but enhances the functional behavior of the ceramic system, specifically at <i>x</i> = 0.15 wt%Mn. Compared to pure CBT and CBTNF ceramics, CBTNF:0.15Mn has demonstrated a highly dense relative density (~96%), a saturated polarization (<i>P_S</i>) of 15.89 µC/cm², a storage energy density (<i>W_ST</i>) of ~1.82 J/cm³, an energy-conversion efficiency (<i>ƞ</i>) of ~51% and an upgraded piezoelectric behavior (<i>d₃₃</i>) of 27.1 pC/N at room temperature. Sharp temperature-dependent dielectric constant (<i>ε_r</i>) peaks display the solid ferroelectric behavior of the CBTNF:0.15Mn sample with a Curie temperature (<i>T_C</i>) of 766 °C. The thermally stable piezoelectric performance of the CBTNF:0.15Mn ceramic was observed at 600 °C, with just a 0.8% <i>d₃₃</i> loss (25 pC/N). The achieved results signify that multi-valence Mn ions have effectively intercalated at the lattice sites of the pseudo-tetragonal phased CBTNF counterpart and enhanced the multifunctional properties of the ceramic system, proving it to be a durable contender for utilization in energy-storage applications and stable high-temperature piezoelectric applications.