The requirements for heteroepitaxial growth of Sb on both GaSb and GaAs, and the subsequent growth of GaSb on Sb, using molecular‐beam epitaxy are described. These systems serve as examples of the heteroepitaxy of group‐V elements with III‐V compounds, i.e., between materials utilizing different bonding and possessing different electronic properties. The quality of the films was determined using high‐resolution four‐circle x‐ray diffraction, and comparisons were made between different structures. GaSb was found to grow (111) oriented on Sb (111) with an inverted stacking sequence. A simple epitaxial model is proposed to explain this. ©1995 American Institute of Physics.