The divalent state of Ln(Ⅲ) ions has attracted much interest because of their ability to serve isomorphously in many biological sys-tem of divalent Ca(II) ion. Therefore, present paper deals with the study of divalent state of Eu(Ⅲ) and Nd(Ⅲ) ions in non-aqueous medium. In present study, cyclic voltammetry and chronopotentiometry were utilized to establish the divalent state of Eu(Ⅲ) and Nd(Ⅲ) ions. The cy-clic voltammetric technique showed two-step reduction process at cathode for both Ln(Ⅲ) ions under specified experimental conditions and chronopotentiometric method also showed two different transition times (). Looking to the shape of cyclic voltammogram we calculated het-erogeneous forward rate constant (K0fh, cm/s) and diffusion coefficient (D, cm2/s) for both ions, which suggested that sweep rate had great ef-fect on the shape of cyclic voltammogram of Eu(Ⅲ) and Nd(Ⅲ) ions. The result of chronopotentiometry also suggested that stable divalent states of Eu(Ⅲ) and Nd(III) ions existed with chronopotentiogram with two distinct transition times. The diffusion coefficients (D, cm2/s) were calculated from Sand equation. The diffusion coefficients of both techniques were compared and the results suggested that the system at electrode surface was changing from being reversible to irreversible. The divalent state of Ln (III) ions has a lot of interest due to their ability to serve isomorphously in many biological sys-tem of divalent Ca (II) ion. In present study, cyclic voltammetry and chronopotentiometry were utilized to establish the divalent state of Eu (III) and Nd (III) ions. The cy-clic voltammetric technique showed two-step reduction process to cathode for both Ln (III) ions under specified experimental conditions and chronopotentiometric method also showed two different transition times (). Looking to the shape of cyclic voltammogram we calculated het-erogeneous forward rate constant (K0fh, cm / s) and diffusion coefficient (D, cm2 / s) for both ions, which suggested that the sweep rate had great ef-fect on the shape of cyclic voltammogram of Eu (III) and Nd (III) ions. The result of chronopotentiometry also suggested that stable divalent states of Eu (Ⅲ) The diffusion coefficients of both techniques were compared with the results suggested that the system at electrode surface was changing from being reversible to irreversible