Electrochemical reaction between K4[Fe(CN)6] and K3[Fe(CN)6] on glass electrodedeposited with In2O3 was studide with graze ellipsometry combined with cyclic voltammetry. Theresults indicated that graze ellipsometry possessed not only time-resolved function, but also space-resolved function. Graze ellipsometrical parameters refiected some information of physicochemicalproperties of interface and diffusion layer near the electrode surface. Change of the pattern of thegraze ellipsometric parameters represented change of rules of the physicochemical properties. Andthe rules revealed the order to random situation of the particles’ distribution near the electrodesurface and were helpful to analyze the properties of the diffusion layer reliably.