Dissolved organic carbon (DOC) and inorganic carbon (DIC and pCO2), lignin biomarkers and the optical properties of dissolved organic matter (DOM) were measured in a gradient of streams and rivers within the Congo Basin (Republic of Congo), with the aim of examining how vegetation cover and hydrology influences the composition and concentration of exported fluvial carbon (C). Three sampling campaigns (February 2010, November 2010 and August 2011) spanning 56 sites are compared by sub-basin watershed land cover type (savannah, tropical forest, and swamp) and hydrologic regime (high, intermediate, and low). Land cover properties predominately controlled the amount and quality of DOC, chromophoric DOM (CDOM) and lignin phenol concentrations (∑8) exported in streams and rivers throughout the Congo Basin. Higher DIC concentrations and changing DOM composition (lower molecular weight, less aromatic C) during periods of low hydrologic flow indicated a shift from rapid overland supply pathways in wet conditions to deeper groundwater inputs during drier periods. Lower DOC concentrations in forest and swamp sub-basins were apparent with increasing catchment area, indicating enhanced DOC loss with extended water residence time. Surface water pCO2 in savannah and tropical forest catchments ranged between 2600 and 11922 µatm, and swamp regions contained extremely high pCO2 (10598-15802 µatm), highlighting their potential as significant pathways for water-air efflux. Our data suggest that the quantity and quality of DOM exported to streams and rivers is largely driven by terrestrial ecosystem structure and that anthropogenic land-use or climate change may impact the composition and reactivity of fluvial C, with ramifications for regional C budgets and future climate scenarios.