To design properly and optimizate liquid-assisted processes such as reactive infiltration for fabricating light weight and corrosion resistant SiC/TiSi2 composites, the interfacial phenomena taking place when liquid Si-rich Si-Ti alloys are in contact with glassy carbon (GC) were investigated for the first time by wetting tests performed by both the sessile and pendant drop methods at T = 1450°C. Specifically, two different Si-rich Si-Ti alloys were selected, and the obtained results in terms of contact angle values, spreading kinetics, reactivity, and developed interface microstructures were compared with experimental observations previously obtained for the liquid Si-rich Si-Ti eutectics processed under the same operating conditions. The increase of the Si content did not affected the final contact angle values. Contrarily, the final developed microstructure at the interface as well as the spreading kinetics were observed as weakly dependent on the composition. From the practical point of view, Si-Ti alloy compositions with a Si-content falling in the simple eutectic region of the phase diagram might be potentially used as infiltrant materials of C- and SiC-based composites.