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Comprehensive Summary The trifluoromethoxy functional group has received increasing attention in recent years due to its distinctive properties such as good metabolic stability, appropriate lipophilicity and special electrical properties. Thus, the development of new reagents and new strategies of direct trifluoromethoxylation are attracting the enthusiasm of many fluorine chemical workers. At present, nucleophilic and radical trifluoromethoxylating reagents have made major breakthroughs, greatly promoting the development of trifluoromethoxy chemistry. This review is mainly divided into two parts: nucleophilic and radical types, focusing on the development history, characteristics and applications of various trifluoromethoxylating reagents.