Physical properties of rubber compounds are affected by the filler-rubber interaction, filler dispersion in the rubber matrix, and crosslink structure formed during vulcanization. Organosilane agents are essentially used in silica-rubber compounds to inhibit the formation of silica agglomerates and increase the formation of silica-rubber networks. Generally, organosilane agents have an alkoxysilyl alkyl sulfide structure and are classified into silane coupling and covering agents depending upon the presence of sulfur. Coupling agents have a sulfur moiety and serve as a sulfur donor during the vulcanization process, thus increasing the formation of filler-rubber and chemical crosslink networks. On the other hand, covering agents promote the hydrophobation of silica surfaces, decreasing the adsorption loss of vulcanization additives, which increases the formation of chemical crosslink networks. This implies that organosilane agents can affect the vulcanizate structure, which causes a variation in the properties of silica compounds. Therefore, in this study, the effect of coupling (bis(3-triethoxysilylpropyl)disulfide (TESPD) and bis(3-triethoxysilylpropyl)tetrasulfide (TESPT)) agents and a covering (triethoxy(octyl)silane) agent on the vulcanizate structure and properties of silica compounds was investigated and compared. In the comparative study of coupling and covering agents, the influence of sulfur donors on the formation of vulcanizate structures was investigated. In the case of the coupling agents, the effect of sulfur rank on the vulcanizate structure and properties of silica-rubber compounds was quantitatively analyzed through various characterization techniques.