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The electrocatalytic activity of electrode materials synthesized by anodic selective dissolution of Ag–Pd alloys based on silver (4 and 8 at % Pd) was studied. Kinetic regularities of formic acid electrooxidation on palladium and anodically modified Ag–Pd alloys in an acidic sulfate solution have been established. The process includes the diffusion of HCOOH, its dissociative chemisorption, and irreversible ionization of atomic hydrogen. The conditions for formic acid anodic oxidation on Pd and Ag–Pd alloys were determined depending on the composition of the electrode system and the mode of preliminary electrochemical modification (selective dissolution) of the alloy using transient electrochemical measurements. The role of the surface development of an alloy in the kinetics of anodic degradation of formic acid was revealed. It was shown that the selective dissolution of Ag–Pd alloys contributes to a noticeable increase in the rate of the kinetic stage of atomic hydrogen ionization. A necessary condition for the activation of the anodically modified alloy in relation to the electrooxidation of HCOOH is the excess of both critical parameters (charge and potential) corresponding to the onset of morphological development and phase transformations in the surface layer of the Ag–Pd systems. [ABSTRACT FROM AUTHOR]