High crystalline quality GaAs/Ge/GaAs heterostructures have been grown on both straight and slightly misoriented GaAs(100) substrates by molecular beam epitaxy. High‐energy electron diffraction was used to study the sublattice rotation of GaAs on epitaxial Ge dependent on the use of a Ga or As prelayer. On straight (100) substrates, a Ga prelayer was observed to rotate the GaAs surface reconstruction by &pgr;/2 while an As prelayer preserved the GaAs orientation observed prior to Ge deposition. No rotation of the surface was observed on substrates tilted 4° towards [011]. We present a growth model to explain these results.