The nanocrystalline Bi2O3-Y2O3 solid electrolyte material was synthesized by pressureless reactive sintering process with Bi2O3 and Y2O3 nano mixed powder as raw materials, which was prepared by a chemical coprecipitation process. The study on the behavior of nano δ-Bi2O3 formation and its grain growth showed that the solid solution reaction of Y2O3 and β-Bi2O3 to form δ-Bi2O3occurs mainly in the initial stage of sintering process, and nano δ-Bi2O3 crystal grains grow approximately following the rule of paracurve ((D-D0)2=K.t) during sintering process. After sintered at 600℃ for 2 h, the samples could reach above 96% in relative density and have dense microstructure with few remaining pores, the δ-Bi2O3 grains are less than 100 nm in size.