The focus of this dissertation is on the fundamental understanding of how AAEMs operate. Both electrochemical and physical studies were conducted in ex-situ and in-situ environments. Most of the studies were conducted on novel AAEM materials provided by collaborators of the Coates group at Cornell University. Both ammonium and phosphonium functionalized AAEMs were studied. Studies address anion exchange dynamics and swelling of the AAEMs using the electrochemical quartz crystal microbalance (EQCM) technique. Acoustic impedance analysis was utilized to understand the viscoelasticity of the membrane material. The subsequent studies explore the transport properties under different conditions and making use of different electrocatalysts that have shown promising oxygen reduction reaction (ORR) activity. Lastly, the morphology of the AAEMs was studied using transmission electron microscopy, small angle x-ray scattering (SAXS) and conducting probe atomic force microscopy (Cp-AFM). In an attempt to uncover the morphology of the AAEMs, the visual formation of carbonate formation was visualized using the insitu-TEM technique.