Polymerizable monomer conjugated linoleic acid (CLA) and its ionized species (soap) were employed as raw materials to construct CLA-Ufasomes through pH-induced self-assembling in aqueous solution. Subsequently, CLA-Ufasomes self-assembled at high concentration were chemically tethered by intra-ufasomal self-crosslinking of conjugated double bonds in the CLA molecules through thermal polymerization to obtain the stable CLA-FAV. The morphologies and size distribution were characterized by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The experimental results indicated that the morphology of the CLA-FAV prepared through thermal polymerization was consistent with that of the CLA-FAV obtained by UV irradiation at pH 8.6. Moreover, the CLA-FAV with diameter of 10-20 nm were always obtained in a wide concentration range of 3-100 mmol?L-1 (500 times of critical vesicular concentration of CLA). Finally, the in vitro release results of 5-fluorouracil (5-FU) showed that the CLA-FAV self-crosslinked through thermal polymerization possessed a good effect on encapsulation and release of 5-FU.