The grain boundary effect on the ionic conductivity was investigated using a.c. admittance analysis in (Bi2O3)0.715(CaO)0.285 oxygen-ion conducting solid electrolyte. As a separated arc representing grain boundary polarization was not observed in the admittance plane, bulk conductivity was measrued for samples with various grain sizes in the temperature range from 48$0^{circ}C$ to 72$0^{circ}C$ and the conductivity distribution between grain interior and grain boundary was determined by the reported analytical methods. In the above temperature range, grain boundary worked as a high conductive path instead of blocking layer and ionic conduction through grain boundary was significant. The activation energy for conduction through grain and grain boundary was 78 and 106 kJ/mol, respectively.