Innovations in nanofabrication have expedited advances in hollow‐structured nanomaterials with increasing complexity, which, at the same time, set challenges for the precise determination of their intriguing and complicated 3D configurations. Conventional transmission electron microscopy (TEM) analysis typically yields 2D projections of 3D objects, which in some cases is insufficient to reflect the genuine architectures of these 3D nano‐objects, providing misleading information. Advanced analytical approaches such as focused ion beam (FIB) and ultramicrotomy enable the real slicing of nanomaterials, realizing the direct observation of inner structures but with limited spatial discrimination. Electron tomography (ET) is a technique that retrieves spatial information from a series of 2D electron projections at different tilt angles. As a unique and powerful tool kit, this technique has experienced great advances in its application in materials science, resolving the intricate 3D nanostructures. Here, the exceptional capability of the ET technique in the structural, chemical, and quantitative analysis of hollow‐structured nanomaterials is discussed in detail. The distinct information derived from ET analysis is highlighted and compared with conventional analysis methods. Along with the advances in microscopy technologies, the state‐of‐the‐art ET technique offers great opportunities and promise in the development of hollow nanomaterials. Electron tomography (ET) serves as a unique and powerful tool kit, offering distinctive 3D information of intricate nanostructures. The exceptional capability of the ET technique in the structural, chemical, and quantitative analysis of hollow‐structured nanomaterials is showcased. Mediated by the ET technique, an in‐depth understanding toward nanomaterials' synthesis and their structure–performance relationship is further revealed.