In this study, a solid-state approach was utilized to synthesize Ba0.54Na0.46Nb1.29W0.37O5 ceramic material. The crystal structure of the synthesized material was examined through X-ray diffraction, with further refinement carried out using the Rietveld method. The analysis revealed that the material exhibited a crystal structure resembling tungsten tetragonal bronze. The determined cell parameters were found to be a = b = 12.37813 ± 0.02 Å and c = 3.93552 ± 0.02 Å, with a space group of P4bm. Electrical investigations were conducted via impedance spectroscopy across a frequency range from 1 Hz to 1 MHz, and a temperature range from ambient to 550 °C. The analysis of the impedance data indicated a distinct non-Debye conductivity relaxation behavior within this crystalline phase. Interestingly, the electrical response was attributed to dual contributions from both the grains and their boundaries, as well as the electrodes.