A multi-constituent co-assembling route is used to synthesize ordered mesoporous thiol-functionalized hybrid materials, which involves the co-assembly of 3-thiolpropyltrimethoxysilane, TEOS, low-polymerized phenolic resols and triblock copolymer. The XRD, N₂ sorption isotherms and TEM techniques reveal that the functionalized hybrid materials have the highly ordered 2-D hexagonal mesostructure, high surface areas (198–466 m²/g), large pore volumes (0.18–0.89 cm³/g) and large pore diameters (4.0–7.8 nm). The XPS, NMR, EDX, FT-IR, and elemental analysis indicate that the matrix is composed of polymer, silica and thiol groups. The organic thiol groups are chemically accessible which can be further oxidized to sulfonic acid groups. Both the polymer and thiol group contents can be tuned by adjusting the amount of each raw material in the initial solution. The thiol group content can reach 3.79 mmol/g in the hybrid ordered mesoporous material. The adsorption ability for metal ions in water of ordered mesoporous thiol-functionalized hybrid materials has also been studied. A high capacity in adsorbing heavy metal ions of Ag⁺ (up to 2.11 mmol/g) and Pb²⁺ (up to 1.60 mmol/g) is observed.