The effects of alkyl chain length of anionic fluorinated fatty acid surfactants, CnF2n+1COOH (n = 7-11), mixed with one cationic hydrocarbon surfactant, tetradecyltrimethylammonium hydroxide (TTAOH), on the formation of polyhedral vesicle gels were investigated in aqueous solutions. On the basis of phase behavior mapping, C8F17COOH, C9F19COOH, C10F21COOH and C11F23COOH except C7F15COOH all formed polyhedral vesicle gels when they were mixed with TTAOH under certain mixed ratios, which was demonstrated by freeze-fracture transmission electron microscopy (FF-TEM) measurements. Meanwhile, the following observation was not observed: the longer the fluorinated alkyl chain, the more effective the formation of gels by fluorinated fatty acids. The formation of the faceted vesicle gels was determined both by the rigidity of the fluorinated alkyl chain and the co-crystallization of fluorocarbon chains and hydrocarbon chains, as revealed by the results of differential scanning calorimetry (DSC), wide angle X-ray scattering (WAXS) and 19F NMR measurements. Furthermore, the polyhedral vesicle gels showed high viscoelasticity, which increased clearly with increasing fluorinated alkyl chain length, indicating that the viscoelastic property of the polyhedral vesicle gel was a result of the crystalline state of the polyhedral vesicle bilayers at room temperature. As far as we know, such polyhedral vesicle gels formed from perfluorinated and hydrocarbon surfactant mixtures have been rarely reported. Our study can be a great advancement in fundamental research of surfactant vesicle gels.