Layering AgNO3 in alcohol onto octavinylsilsesquioxane (OVS) in CHCl3 results in a one-dimensional coordination polymer, {Ag-4(NO3)(4)(OVS).solvents)(n) (SD/Ag4a-d), consisting of unprecedented flat weakly bonded Ag-4(NO3)(4) alternating with the firmly covalent OVS through Ag-1-pi(C=C) bonds. The preferential assembling medium for SD/Ag4a is proven to be alcohols, where a 4:1 silver-OVS adduct is detected by electrospray ionization mass spectrometry. The present outcomes may assist our knowledge of particular interactions for supramolecular architectures of a polynuclear silver system built from OVS containing eight pendent olefin tails.