In this work, a new porous solid polysiloxane material with thiol-amine-based multiple functional groups polysiloxane-(monoamine-thiol) triacetate, P-(N-S)-TrEA (where P- represents [Si-O](n) polysiloxane network), was synthesized using one-pot reaction of TEOS with 3-iminodiethylacetatepropyltrimethoxysilane and 3-thiolethylacetatepropyltrimethoxysilane in the presence of CTAB as a surfactant. Its ethylenediamine and diethylenetriamine-modified polysiloxane-(monoamine-thiol)-tris(N-2-aminoethylacetamide), P-(N-S)-TrEA-NN, and polysiloxane-(monoamine-thiol)-tris(N-3,6-diazahexylacetamide), P-(N-S)-TrEA-NNN, chelating ligand systems were also obtained. The previously reported simple functionalized polysiloxane (monoamine-thiol) has been modified to obtain thiol-monoamine-based multiple functional groups. A variety of methods and techniques including FTIR, solid-state C-13 NMR, XPS and TGA have been used for establishing their structure.