The demand for high-temperature endurable dielectric materials with higher thermal stability in electronic systems operating under extreme temperatures sets a significant channel for the electronic industry. This work focuses on the dielectric and impedance behavior for lead-free Ba1−xNd2x∕3Zr0.1Ti0.9O3 (BNZT); (0.00 ≤x≤ 0.04) between 300 ∘C – 400 ∘C and synthesized by conventional solid-state reaction method at optimum temperatures. Structural characterizations confirmed the tetragonal (P4mm symmetry) structure formations for the BNZT ceramics. XPS analysis confirmed the Nd-substitution at the Ba-site in the BNZT ceramics. FE-SEM study showed grain growth reduction with enhanced grain boundaries. The dielectric study showed lower dielectric loss with enhanced dielectric permittivity at high temperatures. Impedance analysis confirmed the negative temperature coefficient of resistance (NTCR) and non-Debye type behavior with higher thermal stability. Singly-ionized oxygen vacancies mainly govern the conduction process in BNZT ceramics. Enhanced dielectric and impedance properties suggest that Nd-substituted BNZT electroceramics are promising materials for applications in high-temperature-based energy storage systems.