More and more controlled polymerization methodologies have been developed in the last decades. However, great challenges still remain in chemoselective polymerizations for advanced polymer precision synthesis. Traditionally, polymerizations in the presence of multifunctional initiators or monomers with more reactive groups suffer from ill-defined products, low efficiency and tedious synthetic steps. Meanwhile, chemoselective copolymerizations from a mixed monomer feedstock is a long-term goal for synthesis of block and multiblock copolymers. Based on the development of novel catalysis, microflow technology, and switchable strategy in the absence/presence of external-stimuli, significant progress has been achieved in chemoselective polymerizations. In this review, chemoselective homopolymerizations (multifunctional initiators and multifunctional monomers) and copolymerizations (mixed monomers and mixed mechanisms) are highlighted in order. The future challenges and opportunities are proposed with the aim to provide the insight into further development of chemoselective polymerizations and advanced polymer precision synthesis.

在过去的几十年中，越来越多的受控聚合方法学被开发出来。然而，用于高级聚合物精确合成的化学选择聚合仍然面临巨大挑战。传统上，在具有更多反应性基团的多功能引发剂或单体的存在下进行聚合会产生不确定的产物，低效率和繁琐的合成步骤。同时，来自混合单体原料的化学选择性共聚是合成嵌段和多嵌段共聚物的长期目标。基于在不存在/存在外部刺激的情况下新型催化，微流技术和可切换策略的发展，化学选择性聚合已取得了重大进展。在这篇评论中，依次突出了化学选择性均聚（多功能引发剂和多功能单体）和共聚（混合单体和混合机理）。提出了未来的挑战和机遇，旨在为化学选择性聚合和高级聚合物精密合成的进一步发展提供见识。