In this study, the Ho-substituted BaZrO3 electrolyte ceramics (BaZr1-xHoxO3-δ, 0.05 ≤ x ≤ 0.20) were synthesized through a low-cost flash pyrolysis process followed by conventional sintering. The effects of Ho-substitution in BaZrO3 studied in terms of the structural phase relationship, microstructure and electrical conductivity to substantiate augmented total electrical conductivity for intermediate temperature solid oxide fuel cells (IT-SOFCs). The Rietveld refined X-ray diffraction (XRD) patterns revealed that pure phase with [Formula: see text] space group symmetry of cubic crystal system as originated in all samples sintered at 1600 °C for 8 h. The Raman spectroscopic investigations also approved that Ho incorporation in BaZrO3 ceramics. Field Emission Scanning Microscopic (FESEM) study informed a mixture of fine and coarse grains in the fracture surface of Ho-substituted BaZrO3 sintered samples. The relative density and average grain size of samples were observed to decrease as per the addition of Ho-substitution in BaZrO3 ceramics. The electrical conductivity study was accomplished by Electrical Impedance Spectroscopy (EIS) under 3% humidified O2 atmosphere from 300 to 800 °C. Furthermore, the total electrical conductivity of BaZr0.8Ho0.2O3-δ ceramic was found to be 5.8 × 10-3 S-cm-1 at 600 °C under 3% humidified atmosphere, which may be a promising electrolyte for IT-SOFCs.