Controls on chemical weathering, such as bedrock geology, runoff, and temperature, are considered to be the primary drivers of Si transport from the continents to the oceans. However, recent work has highlighted terrestrial vegetation as an important control over Si cycling. Here we show that at the regional scale (Southern New England, USA), land use/land cover (LULC) is an important variable controlling the net transport of Si from the land to the sea, accounting for at least 40% of dissolved Si (DSi) fluxes. A multiple linear regression model using average DSi fluxes from 25 rivers (>2,300 observations) shows the percent forest cover, as well as development and agricultural land use, to be significant (p < 0.05) drivers of DSi flux. This was true regardless of watershed size and lithology. Furthermore, forest cover is significantly negatively correlated, while development is significantly positively correlated, with Si concentrations and fluxes. We hypothesize that these relationships are due to several mechanisms, specifically the ability of terrestrial vegetation to store large amounts of Si within its biomass, the altered watershed hydrology that accompanies LULC change, and the capability of urban regions to serve as sources of Si to aquatic systems. Thus, we conclude that anthropogenic activities may be directly perturbing the global Si cycle through land use change and we offer a conceptual model which highlights a new approach to understanding the non-geochemical controls on Si fluxes.