The effects of climate and environmental change are likely to exacerbate water stress in Africa over the next five decades. It appears obvious, therefore, that large river basins with considerable total renewable water resources will play a prominent role in regional cooperation to alleviate the pressure of water scarcity within Africa. However, managing water resources in the large river basins of Africa involves problems of data paucity, lack of technical resources and the sheer scale of the problem. These river basins are located in regions that are characterized by poverty, low levels of economic development and little food security. The rivers provide multiple goods and services that include hydro-power, water supply, fisheries, agriculture, transportation, and maintenance of aquatic ecosystems. Sustainable water resources management is a critical issue, but there is almost always insufficient data available to formulate adequate management strategies. These basins therefore represent some of the best test cases for the practical application of the science associated with the Predictions in Ungauged Basins (PUB). The thesis presents the results of a process-based hydrological modelling study in the Congo Basin. One of the primary objectives of this study was to establish a hydrological model for the whole Congo Basin, using available historical data. The secondary objective of the study was to use the model and assess the impacts of future environmental change on water resources of the Congo Basin. Given the lack of adequate data on the basin physical characteristics, the preliminary work consisted of assessing available global datasets and building a database of the basin physical characteristics. The database was used for both assessing relationships of similarities between features of physiographic settings in the basin (Chapters 3 and 4), and establishing models that adequately represent the basin hydrology (Chapters 5, 6, and 7). The representative model of the Congo Basin hydrology was then used to assess the impacts of future environmental changes on water resources availability of the Congo Basin (Chapter 8). Through assessment of the physical characteristics of the basin, relationships of similarities were used to determine homogenous regions with regard to rainfall variability, physiographic settings, and hydrological responses. The first observation that comes from this study is that these three categories of regional groups of homogenous characteristics are sensible with regards to their geographical settings, but the overlap and apparent relationships between them are weak. An explanation of this observation is that there are insufficient data, particularly associated with defining sub-surface processes, and it is possible that additional data would have assisted in the discrimination of more homogenous groups and better links between the different datasets. The model application in this study consisted of two phases: model calibration, using a manual approach, and the application of a physically-based a priori parameter estimation approach. While the first approach was designed to assess the general applicability of the model and identify major errors with regard to input data and model structure, the second approach aimed to establish an understanding of the processes and identify useful relationships between the model parameters and the variations in real hydrological processes. The second approach was also designed to quantify the sensitivity of the model outputs to the parameters of the model and to encompass information sharing between the basin physical characteristics and quantifying the parameters of the model. Collectively, the study’s findings show that these two approaches work well and are appropriate to represent the real hydrological processes of Congo Basin. The secondary objective of this study was achieved by forcing the hydrological model developed for the Congo Basin with downscaled Global Climate Model (GCMs) data in order to assess scenarios of change and future possible impacts on water resources availability within the basin. The results provide useful lessons in terms of basin-wide adaptation measures to future climates. The lessons suggest that there is a risk of developing inappropriate adaptation measures to future climate change based on large scale hydrological response, as the response at small scales shows a completely different picture from that which is based on large scale predictions. While the study has concluded that the application of the hydrological model has been successful and can be used with some degree of confidence for enhanced decision making, there remain a number of uncertainties and opportunities to improve the methods used for water resources assessment within the basin. The focus of future activities from the perspective of practical application should be on improved access to data collection to increase confidence in model predictions, on dissemination of the knowledge generated by this study, and on training in the use of the developed water resources assessment techniques.