Ordered mesoporous silica-based materials with various mesostructures are generally synthesized from hydrocarbon surfactants. In this review, I have briefly summarized recent developments of syntheses of ordered mesoporous silica-based materials templated from fluorocarbon–hydrocarbon surfactant mixtures and semi-fluorinated surfactants. The novel templates of fluorocarbon–hydrocarbon surfactant mixtures, semi-fluorinated, and fluorinated surfactants offer a good opportunity to synthesize ordered mesoporous silica-based materials with improved stability, highly catalytic activity, tailorable pore sizes, and novel mesostructures.