Silicon (Si) released as H4SiO4 by weathering of Si-containing solid phases is partly recycled through vegetation before its land-to-rivers transfer. By accumulating in terrestrial plants to a similar extent as some major macronutrients (0.1–10% Si dry weight), Si becomes largely mobile in the soil-plant system. Litter-fall leads to a substantial reactive biogenic silica pool in soil, which contributes to the release of dissolved Si (DSi) in soil solution. Understanding the biogeochemical cycle of silicon in surface environments and the DSi export from soils into rivers is crucial given that the marine primary bio-productivity depends on the availability of H4SiO4 for phytoplankton that requires Si. Continental fluxes of DSi seem to be deeply influenced by climate (temperature and runoff) as well as soil-vegetation systems. Therefore, continental areas can be characterized by various abilities to transfer DSi from soil-plant systems towards rivers. Here we pay special attention to those processes taking place in soil-plant systems and controlling the Si transfer towards rivers. We aim at identifying relevant geochemical tracers of Si pathways within the soil-plant system to obtain a better understanding of the origin of DSi exported towards rivers. In this review, we compare different soil-plant systems (weathering-unlimited and weathering-limited environments) and the variations of the geochemical tracers (Ge/Si ratios and δ30Si) in DSi outputs. We recommend the use of biogeochemical tracers in combination with Si mass-balances and detailed physico-chemical characterization of soil-plant systems to allow better insight in the sources and fate of Si in these biogeochemical systems.