Enantioenriched monofluoroalkenes are important structural motifs in life science and functional materials. To date, only limited strategies were reported for the synthesis of monofluoroalkenes with stereogenic carbon centers; the axially chiral counterpart is still highly desirable. Herein, we report Ni-catalyzed defluorinative cross-electrophile coupling of gem-difluoroalkenes with biaryl electrophiles for the synthesis of axially chiral monofluoroalkenes. The resulting axially chiral monofluoroalkenes are formed with excellent regio-and stereoselectivities. Synthetic transformation of these axially enantioenriched monofluoroalkenes was also demonstrated.