Al-Cr and Al-Cr-Si composite cathodes were obtained by the hot compaction of aluminum, chromium, and silicon powder mixtures. The phase transformations in the surface layer of the Al-Cr-Si composite cathodes subjected to the arc heating were considered. The elemental and phase compositions of the modified cathodes’ surfaces were studied using X-ray diffraction, scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). The effect of the silicon addition on the structural evolution in the cathode surface during arc evaporation is shown. It was found that an arc impact on the cathode surface resulted in the melting and consequent crystallization of the multiphase mixture of intermetallic compounds and eutectic in the cathode surface layer. Cathode surface layers were found to be depleted of aluminum and silicon due to the ejection of these elements in drop form from the Al-Si liquid layer on the cathode surface. This can result in the change in the elements ratio in the deposited coating as compared with that in the cathode and thus influence the coated tools’ durability.