Abstract. Spanning over 3000 km in length and with a catchment of approximately 1.4 million km2, the Zambezi River is the fourth largest river in Africa and the largest flowing into the Indian Ocean from the African continent. We present data on greenhouse gas (GHG: carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O)) concentrations and fluxes, as well as data that allow for characterization of sources and dynamics of carbon pools collected along the Zambezi River, reservoirs and several of its tributaries during 2012 and 2013 and over two climatic seasons (dry and wet) to constrain the interannual variability, seasonality and spatial heterogeneity along the aquatic continuum. All GHG concentrations showed high spatial variability (coefficient of variation: 1.01 for CO2, 2.65 for CH4 and 0.21 for N2O). Overall, there was no unidirectional pattern along the river stretch (i.e., decrease or increase towards the ocean), as the spatial heterogeneity of GHGs appeared to be determined mainly by the connectivity with floodplains and wetlands as well as the presence of man-made structures (reservoirs) and natural barriers (waterfalls, rapids). Highest CO2 and CH4 concentrations in the main channel were found downstream of extensive floodplains/wetlands. Undersaturated CO2 conditions, in contrast, were characteristic of the surface waters of the two large reservoirs along the Zambezi mainstem. N2O concentrations showed the opposite pattern, being lowest downstream of the floodplains and highest in reservoirs. Among tributaries, highest concentrations of both CO2 and CH4 were measured in the Shire River, whereas low values were characteristic of more turbid systems such as the Luangwa and Mazoe rivers. The interannual variability in the Zambezi River was relatively large for both CO2 and CH4, and significantly higher concentrations (up to 2-fold) were measured during wet seasons compared to the dry season. Interannual variability of N2O was less pronounced, but higher values were generally found during the dry season. Overall, both concentrations and fluxes of CO2 and CH4 were well below the median/average values for tropical rivers, streams and reservoirs reported previously in the literature and used for global extrapolations. A first-order mass balance suggests that carbon (C) transport to the ocean represents the major component (59%) of the budget (largely in the form of dissolved inorganic carbon, DIC), while 38% of the total C yield is annually emitted into the atmosphere, mostly as CO2 (98%), and 3% is removed by sedimentation in reservoirs.