This work is devoted to the study of the sorption properties of the firstly synthesized the poly(N-thiocarbamoyl-3-(2-aminoethyl) aminopropylsilsesquioxane) with respect to precious metal ions in the conditions of competitive sorption. The study was carried out in static and dynamic versions using the multicomponent solutions with different pH values. The results obtained indicate a high affinity of the studied polysilsesquioxane for Pt4+, Au3+, Ag+, and Pd2+ ions in the multicomponent solutions, in contrast to base metal ions. In static conditions the most complete extraction of Au3+ is observed at pH = 2.5-7, Pt4+ at pH = 4, Pd2+ at pH <4. Ag+ is practically quantitatively extracted in the entire investigated pH range, which makes it possible to selectively separate this ion from the multicomponent systems. Silver (I) ions are quantitatively sorbed on TCAEAPPSS in the presence of foreign ions in the dynamic version of sorption, which in the future will allow the development of methods for the selective extraction of this type of ions from systems of complex composition.