The energy crisis has stimulated a rapid growth of developments in the photovoltaic industry in recent years. To reduce the high cost and the toxicity of classical metallurgical routes, new methods, such as vacuum refining of silicon, have been developed. Moreover, at the industry level, parameters such as the porosity in crucibles and dies are not controlled, so wettability, infiltration, and reaction between silicon and graphite are the key factors in the purification process. In this work, the behavior of several refractory substrates against melted silicon was studied by the classic sessile drop method. The most important phenomena, i.e., wettability and infiltration, were compared with the properties of the substrates. According to the results, for the carbonaceous materials, the reaction of triple line silicon-graphite manages these phenomena, whereas for alumina, a passive layer is formed due to the presence of oxygen, which is subsequently eliminated by the chemical reactions, delaying the process. Regarding the contact angle and infiltration behavior, alumina showed the best results, but due to its reactivity, it contaminates Si, so that this material is not recommended for solar silicon application. However, composite 2 is compatible with the application, as it shows good results in comparison with the other materials.