Tetrakis(aminophenyl)porphyrin with four bixin side chains in statistical orientation with respect to the porphyrin plane and its zinc(II) complex produced stable colloidal solutions in water at pH 9, Cryoelectron microscopy showed spherical unilamellar vesicles with diameters ranging from 30 to 120 nm and a membrane thickness of 4.7 +/- 0.5 nm, corresponding to a monomolecular layer with the bixin side chains tilted by 30 degrees. The stiff vesicle membranes were not sensitive to the addition of sodium chloride and survived adsorption to dry solid surfaces. Furthermore, the vesicles were totally polymerized by visible light, These polymer vesicles remained intact in 95% ethanol, and scanning force microscopy (SFM) images showed perfectly spherical shapes on graphite. A slow collapse is only observed on hydrated mica, The tetrabixinporphyrin also produced stable monolayers on water surface which polymerized upon irradiation. Combination of the polyene vesicle with an electron-accepting porphyrin, namely a synthetic guanidinium porphyrin or 2-anthraquinone sulfonate, led to light-induced long-lived charge separations.