Fluoropolymers have been reduced locally by the radical anion of a redox mediator electrogenerated at a microelectrode operating in the configuration of a scanning electrochemical microscope. Approach curves with different redox mediators were used to investigate the reduction mechanism of the fluoropolymer. Different factors are discussed, such as the monomer reduction mechanism, the kinetic control by the surface modification growth, and the conductivity of the modified surface. The fluoropolymers' reduction parallels the trends observed in organic electrochemistry in solution within the haloalkane series.