Mesoporous silica materials (HS-JLU-20) with an extremely high content of mercaptopropyl groups have been successfully synthesized using fluorocarbon-hydrocarbon surfactant mixtures through a simple cocondensation approach of tetraethyl orthosilicate (TEOS) and (3-mercaptopropyl)trimethoxysilane (MPTS), which are characterized by X-ray diffraction (XRD), nitrogen adsorption and desorption isotherms, transmission electron microscopy (TEM), CHNS elemental analysis, thermogravimetry analysis (TGA), and Si-29 NMR spectroscopy. The results show that HS-JLU-20 samples with molar ratios of MPTS/(MPTS + TEOS) at 0.5-0.8 in the starting synthetic gels still show their mesostructures, while HS-SBA-15 with the molar ratio of MPTS/(MPTS + TEOS) at 0.50 completely loses its mesostructure in the absence of fluorocarbon surfactant. Possibly, fluorocarbon surfactant containing N+ species with a positive charge could effectively interact with negatively charged mercapto groups in the synthesis of HS-JLU-20 materials, resulting in the formation of mesoporous silicas with good cross-linking of silica condensation even at an extremely high content of organic mercapto groups. More interestingly, after the treatment with hydrogen peroxide, HSO3-JLU-20 materials with an extremely high content of organic sulfonic groups exhibit comparable activity with liquid concentrated sulfuric acid in catalytic esterification of cyclohexanol with acetic acid.