Introduction of fluorine into organic molecules often causes significant changes in their physical, chemical and biological properties, which result in the wide application of fluorine-containing compounds in many fields of chemistry such as drug discovery, agrochemical development and material science. As a consequence, rapid assembly of fluorinated structures has become one of the most popular research topics in the past decade, which also propelled eminent breakthroughs in related areas. Generally, fluorination methods could be divided into two types according to the fluorinating reagent used, i.e., electrophilic fluorination and nucleophilic fluorination. Compared with electrophilic fluorination, the reagents used in nucleophilic fluorination are usually advantageous in economy and availability. In addition, mild conditions employed in nucleophilic fluorination also result in wide substrate scope and excellent functional group compatibility. By resorting to transition- metal and photoredox catalysis, as well as visible light promoted reactions, the authors’ research group has recently established a series of selective fluorofunctionalization of unsaturated carbon-carbon bonds with nucleophilic fluorine sources, affording a panel of structurally novel fluorine(s)-embedded molecules. In this account, the authors have systematically summarized their recent work in this area, challenges and directions which deserve future endeavors in this field are also discussed.