摘要:SummaryElectrocatalysis offers a promising strategy to take advantage of the increasingly available and affordable renewable energy for the sustainable production of fuels and chemicals. Attaining this promise requires a molecular level insight of the electrical interface that can be used to tailor the selectivity of electrocatalysts. Addressing this selectivity challenge remains one of the most important areas in modern electrocatalytic research. In this Perspective, we focus on the use of in situ techniques to bridge the gap in the fundamental understanding of electrocatalytic processes. We begin with a brief discussion of traditional electrochemical techniques, ex situ measurements and in silico analysis. Subsequently, we discuss the utility and limitations of in situ methodologies, with a focus on vibrational spectroscopies. We then end by looking ahead toward promising new areas for the application of in situ techniques and improvements to current methods.Graphical AbstractDisplay OmittedChemistry; Electrochemistry; Electrochemical Energy Conversion; Surface Chemistry; Energy Materials