The development of electrolyte with high-safety and high-voltage is of significant importance for high performance lithium-ion batteries. Recently, organosilicon electrolytes with unique physicochemical properties have become one of the choices. In this review, the advances of organosilicon compounds both as electrolyte solvents and additives are reviewed from the viewpoint of molecular engineering. The design and performance of organosilicon compounds with carbonate group, carbamate group, nitrile group, ionic liquids group and fluoro substitute as high-voltage and high-safety solvent are described in detail. The versatile organosilicon compounds evaluated as high voltage additive, high safety additive, high/low temperature additive, suppression self discharge additive and acid/water scavenger additive are introduced based on their functional group and reaction mechanism. Research trend and prospects of organosilicon electrolyte are presented finally.