Fuel cells are a sustainable alternative to fossil fuels as they are both more efficient and less polluting than combustion engines. Alkaline anion exchange membrane (AEM) fuel cells in particular offer a cheaper alternative to current, acidic fuel cell technologies which require the use of expensive platinum-group metal catalysts. Despite advances in AEMs in recent decades achieving initial performances comparable to commercial fuel cells, AEMs still lack the long-term performance required. This limitation is due in part to incomplete understanding of how nanoscale membrane architecture governs performance properties including ionic transport, water management, and mechanical durability. Advances in AEM design therefore require nanoscale characterization of their internal organization.Characterization of the internal architecture in polymers is challenging, largely due to their inherently low contrast and radiation sensitivity. While techniques such as conventional transmission electron microscopy and ensemble-averaged X-ray scattering have revealed valuable insights into polymer membrane morphologies, these techniques have failed to directly identify and quantitatively analyze the organization of components including ionic channels and crystalline domains within polymer materials. Here, cryogenic 4D scanning transmission electron microscopy (cryo-4D-STEM) and electron energy loss spectroscopy (cryo-EELS) enable nanoscale spatial mapping of the crystalline morphology and ionic channel networks within AEMs. Although atomic resolution imaging of polymers is not feasible due to their radiation sensitivity, diffraction data can be used to learn about their crystalline structure over a larger area. In this work, 4D-STEM nanobeam diffraction is used to identify crystalline domains merely a few nanometers in size, enabling investigation of how crystalline domain size and distribution influences water management and ionic conductivity in AEMs. Additionally, the analysis of inelastic scattering using cryo-STEM-EELS allowed direct identification of the hydrophilic domains in dry and hydrated AEMs, without the need for elemental staining or other sample modifications. Quantitative analysis of ionic channel architecture, including connectivity and tortuosity, provides insights into how ionic network organization affects conductivity and durability. Together, this work establishes advanced cryogenic electron microscopy as a powerful tool for elucidating structure-property relationships in AEMs and offers design principles for next-generation membranes with improved performance and stability.