Two novel polyoxovanadate (POV)-containing fluorosurfactants, each with two hydrophobic fluorinated "tails" and one nanosized, hydrophilic, rigid POV "head group", are synthesized for the first time. They self-assemble into spherical, bilayer vesicles in acetonitrile/water mixed solvents, as evidenced by systemic studies using laser light scattering (LLS) and electron microscopy techniques. The vesicle sizes demonstrate dynamic change over different solvent compositions mainly as a result of the solvent swelling of the fluorocarbon chains, although the charge number on the POVs changes over the solvent polarity as well.