A review is presented on the work carried out in the authors` laboratory on perfluorinated compounds with surfactant properties (PFS). The aggregation features of both long chain perfluoroalcanoates (ammonium perfluorooctan-oate in particular, APFO) and perfluopolyethers (PFPE) are analyzed with direct spectroscopies such as Nuclear Magnetic Resonance (NMR), Nuclear Magnetic Relaxation Dispersion (NMRD), Small Angle X-Ray and Neutron Scattering (SAXS and SANS, respectively), and with spectroscopies requiring probe molecules, such as Electron Spin Resonance in continuos and pulsed wave (ESR and ESE, respectively). The properties of micellar systems, lamellar phases, and microemulsions are described.