Electron diffraction measurements on (100) GaAs1−xSbxlayers withx≊0.5 grown by organometallic vapor phase epitaxy indicate that ordered phases are formed during growth. Two ordered phases are observed. The simple, tetragonal AuCu‐I type phase consists of alternating {100} oriented GaAs and GaSb layers. Only the two variants with the tetragonalcaxes perpendicular to the growth direction are observed. At least two variants are observed for the chalcopyriteE11structure with alternating {210} oriented GaAs and GaSb layers.