According to the first principles, we investigate the structure, electronic, and magnetic properties of fluorinated graphene doped with external X (Al, P, Ga, As, Si) atoms at double vacancies, and find that like double vacancy doping of graphene, this kind of the fluorinated graphene divacancy substitution is also an ideal choice for substitutional doping. The results show that the electronic property and magnetic property of the fluorinated graphene both have large changes: the fluorinated graphene doped with Al (Ga) atoms can cause the semiconductor-to-metal transitions and induce magnetic moments. The fluorinated graphene doped with P (As) atoms becomes spin-polarized semiconductor. The Si doped fluorinated graphene keeps the semiconductor properties unchanged and has no magnetic moments. Through the further discussion about the mechanism of magnetism the relation between the doping concentration and magnetic property is obtained, and the magnetic properties in different doping situations are found to be caused by the different orbital electrons of different atoms. The divacancy substitutional doping behaviors enrich not only the doping ways of fluorinated graphene materials, but also its distinctive electronic and magnetic characteristics, which make this doping structure have potential applications in future electronic devices.