Pastes made from OPC and OPC-silica fume blends, previously investigated by use of the direct TMS method, were studied by using the molybdate method in order to determine changes in polymerization of Si-anions due to hydration and pozzolanic reaction and due to attack of leaching. The results confirm that by the progress of hydration, from 50 to 250 days, the share of silicates which cannot be hydrolytically decomposed and complexed through molybdate reaction decreases, thus contributing to the increase of the oligomeric-polymeric fraction of Si-anions. The leaching attack on the cement pastes brought about polymerization of Si-anions in those mixes.