Cubic Al 0.3Ga 0.7N/GaN heterostructures were grown by plasma-assisted molecular beam epitaxy on 3C-SiC (001) substrates. A profile of the electrostatic potential across the cubic-AlGaN/GaN heterojunction was obtained using electron holography in the transmission electron microscope. The experimental potential profile indicates that the unintentionally doped layers show n-type behavior and accumulation of free electrons at the interface with a density of 5.1×10 11/cm 2, about one order of magnitude less than in wurtzite AlGaN/GaN junctions. A combination of electron holography and cathodoluminescence measurements yields a conduction-to-valence band offset ratio of 5:1 for the cubic AlGaN/GaN interface, which also promotes the electron accumulation. Band diagram simulations show that the donor states in the AlGaN layer provide the positive charges that to a great extent balance the two-dimensional electron gas. © 2012 American Institute of Physics.