A hyphenated electrochemical technique consists of the combination of the coupling of an electrochemical technique with a non-electrochemical technique, such as spectroscopical and optical techniques, electrogravimetric techniques, and electromechanical techniques, among others. This review highlights the development of the use of this kind of technique to appreciate the useful information which can be extracted for the characterization of electroactive materials. The use of time derivatives and the acquisition of simultaneous signals from different techniques allow extra information from the crossed derivative functions in the dc-regime to be obtained. This strategy has also been effectively used in theac-regime, reaching valuable information about the kinetics of the electrochemical processes taking place. Among others, molar masses of exchanged species or apparent molar absorptivities at different wavelengths have been estimated, increasing the knowledge of the mechanisms for different electrode processes.