This paper details a method to chlorinate tetraalkyl orthosilicates in the presence of a catalyst using SOCl2 as the chloride source/deoxygenating agent. Several inexpensive catalysts were screened, and it was found that soluble chloride salts performed better than Lewis base catalysts. The optimized reaction employed a widely used and commercially available soluble chloride salt catalyst (e.g., NBu4Cl, 0.4 equiv), 16 equiv of SOCl2, and afforded quantitative yield of SiCl4 after 3 h. As the bulk of the orthosilicate substrate increased, the yield of SiCl4 decreased. A reaction mechanism has been proposed.