Organosilicons are widely used in many chemistry related fields. Given its important role, the chemical syntheses of organosilicon compounds have received considerable attention. Due to outstanding advantages in cost and environmental friendliness, transition-metal-free C-Si bond formation has been widely studied in the past decades and has been emerged as an important alternative to transition-metal-catalyzed C-Si cross-coupling. In this review, the recent developed methods of carbon-silicon bond formation under transition-metal-free conditions are summarized. The discussion is organized according to catalysts (acid catalysis, base catalysis, and radical initiation) and the types of C-Si bonds that formed. In addition, mechanistic discussions of representative reactions and a prospect for future development in this field are also briefly included. Keywords transition-metal-free; C-Si bond formation; organosilicons, green chemistry 硅是地壳中含量第二多的元素(质量分数约 26.4%), 这激励着人类积极探索和利用含硅化合物. 有机硅化合 物一般具有低毒、绝缘等特点, 在过去百年间得到了极 大发展 [1] , 已广泛应用于医药 [2] 、发光材料 [3] 和色谱检 测 [4] 等领域. 在有机合成化学中, 有机硅试剂也有许多 应用, 如用作羰基和羟基的保护基团、不饱和键还原 [5] 、 手性诱导 [6] 、区域选择性控制 [7] 和反应的助催化剂 [8] 等, 还可用作多种反应的底物 [9] , 并已成功地应用在了多个 天然产物 [10] 和药物分子 [11] 等合成中.