A quantum well composed of layered semiconductors and SnSe2 (Eg=1.03 eV) and SnS2 (Eg=2.18 eV) was grown in several steps by van der Waals epitaxy. After each growth step the electronic structure was characterized by ultraviolet and x-ray photoemission spectroscopy. From these measurements, bandbending and the valence-band offset were determined on both sides of the quantum well. The results show that both wells are of the same magnitude, hence indicating commutativity of the band offset. Small interface dipoles (0.11–0.19 eV) were detected at the interfaces, which could be identified as quantum dipoles. © 1999 American Institute of Physics.