Electrolyte stability is one of the foremost challenges in improving the lifetime and operation of lithium-ion batteries. Despite their desirable high conductivity and solvation properties, conventional carbonate electrolytes have low flash points, low thermal stability, and limited electrochemical windows which give rise to significant safety and performance issues. Electrolyte degradation leads to the formation of problematic gaseous products and decomposition species that can trap lithium and increase cell impedance, leading to capacity fade. Silatronix, Inc, with the University of Wisconsin-Madison, has developed a novel class of electrolytes based on organosilicon solvents with decreased flammability, which have displayed enhanced electrochemical stability and reduced gassing. To understand the degradation mechanisms and structural components behind these improved properties, we report thermal, electrochemical, and hydrolytic stability studies of 4 organosilicon electrolytes with varying molecular substituents, and compare these organosilicons with conventional carbonate electrolytes. We identify and quantify thermal hydrolysis and electrochemical degradation electrolyte products via multinuclear NMR. We report insights into the manner by which different substituents affect electrolyte decomposition, and identify several mechanisms in organosilicon electrolytes that seem to inhibit degradation. Elucidation of the mechanisms of degradation for organosilicon electrolytes will help enable the design of future electrolytes with superior performance.