The membrane electrode assembly (MEA) is a key unit of proton exchange membrane (PEM) fuel cells. The MEA materials, structures, components and fabrication technologies have strong effects on the corresponding fuel cell performance. In particular, the catalyst layers, where the electrochemical reactions take place, are the most important components. Over the past several decades, many efforts have been made to develop high performance PEM fuel cells. MEA performance with advanced catalyst layers has been significantly improved by employing different fabrication methods, changing the catalyst layer structures, and using different components. During PEM fuel cell performance optimization, how to evaluate catalyst layers and their corresponding MEAs becomes critical. The major purpose of such an evaluation is to understand the relationship between fuel cell performance and MEA component structures/compositions. Based on this understanding, catalyst layer/MEA optimization with respect to performance can be carried out in terms of materials used, component compositions, and fabrication parameters. Through optimizing the catalyst layers and MEAs, catalyst utilization can be improved, gas diffusion overpotential reduced, and membrane ohmic losses decreased, while water management inside the catalyst layers/MEAs can also be improved. Therefore, catalyst layer/MEA evaluation is a necessary step in fuel cell development. Accordingly, many electrochemical methods have been developed to evaluate the performance of the catalyst layer/MEA. In this review paper, the principles and methods of catalyst layer/MEA evaluation have been introduced, with some detailed analysis.