In this study, novel chitosan/silica composites with different mass ratios were prepared by in-situ hydrolysis using chitosan (from shrimp shell) as a carrier, triblock copolymer (P123) as the structure-directing agent, and ethyl orthosilicate as a silicon source. These nanocomposites were characterized by different techniques, including the FT-IR, XRD, TGA, SEM, TEM and N2 adsorption–desorption. The results indicated that the morphology and properties of composites changed with the introduction of silica. When the CS/TEOS mass ratio was 0.0775, the CS−2/SiO2 composite displayed a coral-like three-dimensional porous structure with specific surface area of 640.37 m2/g and average pore size of 1.869 nm. The adsorption properties for methylene blue (MB) were investigated as well and the CS−2/SiO2 showed better adsorption performance. The removal rate for MB reached 94.01% with absorbents dosage of 6 g/L, initial concentration of 40 mg/L, initial pH value of 7, temperature of 35 °C, and adsorption time of 40 min. The adsorption process well fitted the Langmuir isothermal model and quasi-second-order adsorption kinetics model. The maximum adsorption capacity for MB was 13.966 mg/g based on Langmuir fitting. The surface functional groups of the composites can play an important role in the adsorption. The adsorption mechanism of CS−2/SiO2 on MB involved electrostatic interaction, hydrogen bonding and functional group complexation. In addition, the prepared chitosan/silica composites showed good reusability at six cycles, making them a promising material in the application of removing dyeing wastewater.