There are many fluorinated quaternary carbon structural units in pharmaceuticals and bioactive compounds. Organic chemists are interested in the stereoselective synthesis of fluorinated quaternary carbon structural units. Constructing a fluorinated quaternary carbon stereocenter can be achieved directly and efficiently by the asymmetric catalytic reaction of fluorinated compounds as substrates. This approach aims to construct fluorinated quaternary carbon stereocenters while diversifying the types of fluorinated compounds. This review introduces a series of reactions for synthesizing fluorinated quaternary carbon chiral centers through asymmetric organic catalysis and transition metal catalysis, including alkylation, arylation, Mannich, Michael addition, and allylation reactions. This work will contribute to the development of the synthesis of fluorinated quaternary carbon chiral center-containing compounds in the future.