Electrochemical analysis in charge-transfer science: The devil in the details

It is easy to carry out electrochemical analysis. It is demanding, however, to do it right, as inherent challenges, emerging from details in the data collection and the result interpretation, frequently present themselves. In pertinence to electron–donor–acceptor interactions, herein, we focus on voltammetrically obtained electrochemical potentials and their immense utility for extracting important characteristics of molecular analytes. Recommendations how to address key pending challenges, based on recent developments in electroanalysis and charge-transfer science, accompany the discussions on undesired impacts from irreversibility of oxidation and reduction, supporting electrolytes, choices of reference, liquid junctions, and ‘nonideality’ of molecular shapes. As the wide implications of charge transfer are indisputable, using the tools at our disposal for improving the reliability of electroanalysis is crucial for advancing modern science and engineering.