Na0.5Bi0.5TiO3 (NBT) and its modifications are known to be new lead-free piezo-ceramics materials and are promising candidates for environment friendly devices. An investigation was carried out on auto combustion synthesis of solid solutions (1−x) Na0.5Bi0.5TiO3[NBT]–xBiFeO3 [BF] (x = 0.04, 0.06, 0.08). BNT-BF solid solution was prepared through citrate-nitrate solution combustion route. The pH of the precursor solution was maintain at 5 to 11before combustion took place. All combustion products were calcined at 900oC for 2 hours to examine the effect of pH variation. A considerable change in crystallite sizes is observed with change in pH value