Abstract: Provided herein are new spermicidal compositions that include one or more fluorous surfactants, e.g., non-ionic fluorous surfactants, anionic fluorous surfactants, cationic fluorous surfactants, and combinations thereof. Also provided are methods of preventing fertilization of an ovum, which include a step of contacting at least one spermatozoon with one or more fluorous surfactants. Additionally described herein are methods of preventing infection, which include a step of contacting at least one infectious pathogenic microorganism with one or more fluorous surfactants. Numerous fluorine-containing surfactants are demonstrated to be efficacious as human spermicides.