Complex impedance and photoluminescence properties have been investigated in Na0.5 Bi(1-x) HoxTiO3 x = 0, 0.5, 1, 2 and 3 mol %. The observation of semicircle in the higher temperature regime from the Nyquist plots confirms the Debye type relaxation. Overlapping of normalized Z″ and M″ peaks suggested the long-range relaxation of charge carriers. The grain resistance (Rg) decreased with temperature. The improved insulating character was found for a small concentration (0.5 mol %) of holmium substituted NBT. Additionally, photoluminescence emission peaks associated with the transitions in Ho3+ ions were observed in the visible range. Quenching in photoluminescence intensities was observed in the higher composition (3 mol % Ho3+ substituted NBT) which we surmise as due to the collective impact of concentration quenching and the emergence of higher symmetric orthorhombic phase (Pbnm) within lower symmetric (R3c + Cc) phase. © 2022 Elsevier B.V.