The interfacial reactions between thin films of cobalt and silicon and (100)-oriented GaAs substrates in two configurations, Co/Si/GaAs and Si/Co/GaAs, were studied using a variety of techniques including Auger electron spectroscopy, x-ray diffraction, and transmission electron microscopy. The annealing conditions were 200, 300, 400, 600-degrees-C for 30 min, and rapid thermal annealing for 15 s. It was found that Si layer in the Co/Si/GaAs system acts as a barrier at the interface between Co and GaAs when annealed up to 600-degrees-C. The interfacial reaction between Co and Si is faster than that between Co and GaAs in the system of Si/Co/GaAs. The sequence of compound formation for the two metallizations studied (Co/Si/GaAs and Si/Co/GaAs) depends strongly on the sample configuration as well as the layer thickness of Si and Co (Co/Si atomic ratio). From our results, it is promising to utilize Co/Si/GaAs multilayer film structure to make a CoSi2/GaAs contact, and this CoSi2 may offer an alternative to the commonly used W silicides as improved gate metallurgies in self-aligned metal-semiconductor field effect transistor (MESFET) technologies.