Hollow mesoporous carbon nanospheres doped with fluorine (FHMC) were synthesized for high-performance supercapacitor applications. Monodisperse nanospheres with a copolymeric core-silica shell were produced by charge density matching. The copolymeric chains in the core phase were crosslinked through a Friedel-Crafts reaction, followed by carbonization at 800 °C under a N2 atmosphere to obtain the core-shell (CSC) nanospheres with a carbon core and silica/carbon composite shell. The silica phase of these core-shell nanospheres was etched selectively during the thermal decomposition of Teflon to synthesize the FHMC nanospheres. During the etching process of silica in the shell phase, the surfaces of the nanospheres were doped with fluorine. The BET surface area was increased significantly from 788 m2/g and 1.31 cm3/g for the CSC nanospheres to 1021 m2/g and 2.55 cm3/g for the FHMC nanospheres. The specific capacitance of the FHMC nanospheres prepared was approximately 174 F/g at a current density of 0.5 A/g. The capacity retention after 10000 charge/discharge cycles at a current density of 1 A/g was approximately 93.6%.