Characterizing longârange electric fields and builtâin potentials in functional materials at nano to micrometer scales is of supreme importance for optimizing devices, e.g., the functionality of semiconductor heteroâstructures or battery materials is determined by the electric fields established at interfaces which can also vary spatially. In this study, momentumâresolved fourâdimensional scanning transmission electron microscopy (4DâSTEM) is proposed for the quantification of these potentials and the optimization steps required to reach quantitative agreement with simulations for the GaAs/AlAs heteroâjunction model system are shown. Using STEM the differences in the mean inner potentials (âMIP) of two materials forming an interface and resulting dynamic diffraction effects have to be considered. This study shows that the measurement quality is significantly improved by precession, energy filtering and a offâzoneâaxis alignment of the specimen. Complementary simulations yielding a âMIP of 1.3Â V confirm that the potential drop due to charge transfer at the intrinsic interface is â0.1Â V, in agreement with experimental and theoretical values found in literture. These results show the feasibility of accurately measuring builtâin potentials across heteroâinterfaces of real device structures and its promising application for more complex interfaces of other polycrystalline materials on the nanometer scale.