This paper describes experimental investigations on electroless deposition of silver from an aqueous bath containing AgNO 3 and N 2 H 4 as the precursor for silver and the reductant, respectively. The kinetics and mechanism of the electrochemical oxidation and reduction processes are studied through the partial polarization plots using the concept of mixed potential theory. Behaviors of cathodic and anodic equilibrium potentials were determined with respect to [Ag + ] and [N 2 H 4 ], respectively. Thermodynamic expressions for the mixed potential E m and kinetic expressions for the mixed current i m were derived by considering specific segments in superimposed cathodic and anodic partial polarization curves and from it to understand the mechanism of the process. Due to antibacterial activity, 1-7 high hardness, low coefficient of friction, high reflectivity and high resistivity 8-10 of silver, silver plated polymers have gained increasing application in the field of medicine, 11,12 opto-electronic devices, 13-17 as well as for decoration purposes. Silver plating can be electrolytic or electroless in case of the later, as no electric current is required, there is an equal probability of plating on the area of substrate exposed to the bath leading to uniform plating. Therefore, a number of studies are reported on electroless deposition of silver. [18][19][20][21][22][23][24][25][26] An electroless plating is basically an electrochemical process combining cathodic-and anodic-half reactions together. 27 Thus, electroless silver plating using ammonia as complexing agent and hydrazine as reducing agent occurs as per the following reactions:Overall reaction;Anodic oxidation reaction;Many researchers have studied the mechanism of electroless plating by using simultaneously occurring but interdependent cathodic metal deposition and anodic oxidation of reductant in an electroless process. [28][29][30][31] Though the usefulness of partial polarization curves [32][33][34] to derive the kinetic equation [35][36][37][38] are studied by many researchers still there remains many areas to be explored so as to give a better insight to mechanistic details. There are reports using mixed potential theory on kinetics and mechanism of copper electroless deposition, 39-41 dissolution processes, 36,42-44 electrochemical precipitation process, 45 other oxidation 27 and leaching process. 46,47 However, there is no such reported work in the field of electroless silver deposition. Depending on the concentration of reacting species and reaction parameters, the mixed potential may be positioned in the linear, Tafel or limiting current region of the curves, which gives an idea about the reaction mechanism i.e. whether the reaction is under anodic or cathodic control or under mixed control. 36 An attempt has been made in this paper to explain mechanistic details of electroless silver deposition reaction by using mixed potential theory of Wagner & Traud, [48][49][50][51][52] Nernst diffusion equation, 53 and Butler -Volmer equation. 33,34 Both o...