Concentration-resolved 2D correlation gel permeation chromatography (GPC) has been used to examine the intricate details of the HCl-catalyzed polymerization of a polymeric silane-coupling agent (SCA), triethoxysilyl-terminated polystyrene (TESiPS). The concentration-resolved 2D correlation GPC maps directly reflect the marked difference in the aggregate-aggregate interactions of dilute and concentrated monomeric units, which govern the differences in the polymerized products. There is an optimum concentration of SCA for the enhancement of interfacial strength and subsequent polymerization. Thus, the concentration-resolved 2D correlation GPC technique can be used as a powerful tool for elucidation of aggregate-aggregate interactions and reaction mechanisms in a surface- or interface-enhanced reaction system. It has been shown that the yield value of polymerization products can be improved to a marked extent by choosing a high initial monomer concentration, due to the increase in the production of oligomers. Multiple reaction processes are promoted by the self-assembly of the monomeric and oligomeric components.