An onion-phase (multilamellar vesicular phase or Lalpha-phase) was prepared from salt-free zero-charged cationic and anionic (catanionic) surfactant mixtures of tetradecyltrimethylammonium hydroxide (TTAOH)/lauric acid (LA)/H2O. The H+ and OH- counterions form water (TTAOH + LA --> TTAL + H2O), leaving the solution salt free. The onion-phase solution has novel properties including low conductivity, low osmotic pressure and unscreened electrostatic repulsions between cationic and anionic surfactants because of the absence of salt. The spherical multilamellar vesicles have an average 250 nm radius as measured by freeze-fracture transmission electron microscopy (FF-TEM) and the maximum interlayer distance, i.e., the thickness of the hydrophobic bilayer and the water layer, was calculated to be around 52 nm by small-angle X-ray scattering (SAXS). Extremely hydrophobic C60 fullerene can be solubilized in this salt-free zero-charged aqueous onion-phase. As a typical result, 0.588 mg.mL(-1) (approximately 0.82 mmol.L(-1)) C60 has been successfully solubilized into a 50 mmol.L(-1) catanionic surfactant onion-phase aqueous solution. The weight ratio of fullerene to TTAL is calculated to be around 1:40. Solubilization of C60 in the salt-free catanionic onion-phase solution was investigated by using different sample preparation routes, and a variety of techniques were used to characterize these vesicular systems with or without encapsulated C60. The onion-phase solution changed color from slightly bluish to yellow or brown after C60 was solubilized. 1H and 13C NMR measurements indicated that the C60 molecules are located in the hydrophobic layers, i.e., in the central positions [omega-CH3 and delta-(CH2)x] of the hydrophobic layers of the TTAL onion-phase. Salt-free zero-charged catanionic vesicular aqueous solutions are good candidates for enhancing the solubility of C60 in aqueous solutions and may broaden the functionality of fullerenes to new potential applications in biology, medicine, and materials. Hopefully, our method can also be extended to solubilize functionalized carbon nanotubes in aqueous solutions.