Molecules with di‐ or trichloromethyl group are widely existed in natural products and man‐made structures that represent special activities in pharmaceuticals and agrochemicals. Besides, polychloromethyl‐containing compounds are also high valuable intermediates in organic synthesis and also can be used as functional materials. Therefore, significant efforts have been made toward the incorporation of polychloromethyl groups into certain structures. In this field, a variety of polychloromethyl reagents, such as CH2Cl2, HCCl3, CCl4, TMSCCl3, TMSCCl2H, etc. have been utilized as the di‐ or trichloromethyl sources toward polychloromethylated structures through radical, nucleophilic, and other reaction patterns. In this review, we summarized and discussed the recent achievements in the synthesis of polychloromethylated compounds, mainly focused on the employment of different polychloromethyl reagents. Most of the works we investigated were reported after 2010. Mechanism discussions and outlooks were also given.