We use transmission electron microscopy to characterize the morphology of InGaP epitaxial layers grown by metal‐organic vapor‐phase epitaxy over misoriented GaAs (001) substrates, with a cutoff angle in a range from 0° to 25°. The occurrence of phase separation and CuPt‐type ordered superstructures has been observed. The most ordered configuration has been found to appear in layers grown on 2° off substrates, and the strength of order decreases with increasing the misorientation angle beyond α=2°. Conversely, whereas the phase separation is less evident in the layer grown at 2°, the sample grown with a misorientation of 25° exhibits the most phase separated configuration. The completion between these two phenomena is discussed depending on the misorientation angle.