Electroanalytical techniques can be used to probe molecular interactions by measuring the charge transfer between a small molecule and a soluble or immobilized biopolymer on a sensor surface (using potentiometry or amperometry) and the charge resistance between an attached biopolymer and the sensor in the presence of a soluble ligand (using electrochemical impedance). Compared with other methods, the electrochemical assay is simple, reliable, allows low detection limits, can be done with extensive sensor materials (carbon, metals, coated glass), and can be achieved even in complex matrices. Although different amperometric techniques would be accomplished for this task, the general formalism to get thermodynamic and electrokinetic binding parameters are similar. The chapter outlines how to prospect sensitive compounds to amperometry as a dynamic electrochemical approach and describes an amperometric experiment to obtain binding parameters for alfa-amylase complexed with epigallocatechin. An R-script is given to process the data.