New fluorinated microemulsions (F-MEs) formulated from partially fluorinated solvent–co-solvent mixtures and fluorinated anionic AOT-analogue surfactants are reported. These F-MEs permit incorporation of water into fluorinated solvents, up to a volume fraction ϕ_water ≈ 0.13. Interestingly, phase behavior and structures, determined by small-angle neutron scattering (SANS), parallel many other classical AOT-type microemulsions, both in normal hydrocarbon and in supercritical-CO₂ (scCO₂) solvents. Using these new F-MEs as reaction media, F-capped silver nanoparticles (Ag-NPs) have been synthesized, representing the first reported preparation of F-NPs in fluorous phase microemulsions.