Although biological measurements are constrained by the same fundamental psychometric principles as self‐report measurements, these essential principles are often neglected in most fields of neuroscience, including psychophysiology. Potential reasons for this neglect could include a lack of understanding of appropriate measurement theory or a lack of accessible software for psychometric analysis. Generalizability theory is a flexible and multifaceted measurement theory that is well suited to handling the nuances of psychophysiological data, such as the often unbalanced number of trials and intraindividual variability of scores of event‐related brain potential (ERP) data. The ERP Reliability Analysis Toolbox (ERA Toolbox) was designed for psychophysiologists and is tractable software that can support the routine evaluation of psychometrics using generalizability theory. Psychometrics can guide task refinement, data‐processing decisions, and selection of candidate biomarkers for clinical trials. The present review provides an extensive treatment of additional psychometric characteristics relevant to studies of psychophysiology, including validity and validation, standardization, dimensionality, and measurement invariance. Although the review focuses on ERPs, the discussion applies broadly to psychophysiological measures and beyond. The tools needed to rigorously assess psychometric reliability and validate psychophysiological measures are now readily available. With the profound implications that psychophysiological research can have on understanding brain‐behavior relationships and the identification of biomarkers, there is simply too much at stake to ignore the crucial processes of evaluating psychometric reliability and validity.