We use dissolved silicon together with its “geochemical twin” germanium for the first time as a hydrologic tracer to study water delivery to the stream during storm events in the Rio Icacos watershed, Puerto Rico. Ge and Si were measured on base flow, stormflow, springwater, and soil water samples. Compositions of all of these waters appear to reflect varying contributions from three components, which we attribute to solutes released from bedrock weathering (groundwater), from short-term soil-water interaction (quick soil water), and longer-term soil-water interaction (matrix soil water). Base flow stream waters have high Si and moderate Ge (Ge/Si ratio ∼0.29 μmol/mol), consistent with a predominantly bedrock weathering source as indicated by their similarity with water sampled from springs emerging from the saprolite-bedrock boundary on a hillslope landslide scar. During storm events there is a shift toward more dilute compositions (but higher Ge/Si ratios) similar to those measured on water samples from temporary depression storage and overland flow (quick soil water). Geochemical mass balance shows that 80%–90% of the stream chemistry can be explained by mixing groundwater with this quick soil water composition, which we infer to reflect new water traveling as shallow throughflow. Stream water δ18O values decrease to more negative values typical of precipitation supporting rapid delivery of rainwater to the stream channel during stormflow. The third component, with a Ge-rich composition characteristic of soil matrix water sampled by tension lysimeters, is required to explain higher stream water Ge/Si ratios measured during hydrograph recession. We infer from this an additional, slower, and less dominant pathway for delivery of soil water to the stream channel.