We have studied the growth of Fe and Co films on ZnSe(001) epilayers and GaAs(001) bulk substrates with electron forward scattering in the form of Auger electron diffraction (AED), and with x‐ray photoelectron spectroscopy (XPS) and reflection high energy electron diffraction to determine the mode of film growth and the formation of the interface. The coverage dependence of the AED forward scattering peaks is modeled and compared with the experimental data obtained for these overlayer systems. We find that the growth of Fe on ZnSe(001) at 175 °C proceeds in a predominantly layer‐by‐layer fashion, while a more three‐dimensional growth mode occurs on the oxide‐desorbed GaAs(001) substrate for both Fe and Co overlayers. Deposition of Co on the ZnSe(001) epilayers results in poorly ordered multicrystalline growth. The XPS data show that the metal/ZnSe interface is less reactive than the corresponding interface with the GaAs(001) substrate.