Quantitative analysis of metal cation doping by solid oxide electrochemical doping (SOED) has been performed under galvanostatic doping conditions. A M-beta"-Al2O3 (M = Ag, Na) microelectrode (contact radius: about 10 mum) was used as cation source to attain a homogeneous solid-solid contact between the beta"-Al2O3 and doping target. In Ag doping into alkali borate glass, the measured dopant amount closely matched the theoretical value. High Faraday efficiencies of above 90% were obtained. This suggests that the dopant amount can be precisely controlled on a micromole scale by the electric charge during electrolysis. On the other hand, current efficiencies of Na doping into Bi2Sr2CaCu2Oy (BSCCO) ceramics depended on the applied constant current. Efficiencies of above 80% were achieved at a constant current of 10 muA (1.6 A cm(-2)). The relatively low efficiencies were explained by the saturation of BSCCO grain boundaries with Na. By contrast, excess Na was detected on the anodic surface of ceramics at a constant current of 100 muA (16 A cm(-2)). In the present study, we demonstrate that SOED enables micromole-scale control over dopant amount. (C) 2003 Elsevier Science B.V. All rights reserved.