Mg-based materials are regarded as one of the most promising candidates for hydrogen storage. In order to clarify the relationship between the structures and properties as well as to understand the reaction and formation mechanisms, it is beneficial to obtain useful information about the size, morphology, and microstructure of the studied materials. Herein, the use of scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques for the representation of Mg-based hydrogen storage materials is described. The basic principles of SEM and TEM are presented and the characterizations of the size, morphology observation, phase and composition determination, and formation and reaction mechanisms clarification of Mg-based hydrogen storage materials are discussed. The applications of advanced SEM and TEM play significant roles in the research and development of the next-generation hydrogen storage materials.