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The particle size of electrode materials has a significant influence on the standard electrode potential and the thermodynamic properties of electrode reactions. In this paper, the size-dependent electrochemical thermodynamics has been theoretically investigated and successfully deduced electrochemical thermodynamics equations for nanoparticles electrode. At the same time, the electrode potential and thermodynamical properties of Ag 2 O/Ag nanoparticles electrode constructed by the solid and spherical Ag 2 O nanoparticles with different sizes further testified that the particle size of nanoparticles has a significant effect on electrochemical thermodynamics. The results show that the electrode potential depends on that of the smallest nanoparticle in a nanoparticles electrode which consisted of different particle sizes of nano-Ag 2 O. When the size of Ag 2 O nanoparticles reduces, the standard electrode potentials and the equilibrium constants of the corresponding electrode reactions increase, and the temperature coefficient, the mole Gibbs energy change, the mole enthalpy change and the mole entropy change decrease. Moreover, these physical quantities are all linearly related with the reciprocal of average particle size (r > 10 nm). The experimental regularities coincide with the theoretical equations.