The south-east littoral is one of the most populous and developed regions in China suffering from serious water pollution problems, and the Xian-Jiang Basin in the mid of this region is among the most polluted watersheds. Critical information is needed but lacking for improved pollution control and water quality assessment, among which water environmental capacity (WEC) is the most important variable but is difficult to calculate. In this study, a one-dimensional water quality model combined with a matrix calculation algorithm was first developed and calibrated with in-situ observations in the Xian-Jiang basin. Then, the model was applied to analyze the spatial and temporal patterns of WEC of the entire basin. The results indicated that, in 2015, the total pollutant discharges into the river reached 6719.68 t/yr, 488.12 t/yr, and 128.57 t/yr for COD, NH3-N and TP, respectively. The spatial pattern suggested a strong correlation between these water contaminants and industrial enterprises, residential areas, and land-use types in the basin. Furthermore, it was noticed that there was a significant seasonal pattern in WEC that the dry season pollution is much greater than that in the plum season, while that in the typhoon season appears to be the weakest among all seasons. The WEC differed significantly among the 24 sub-basins during the dry season but varied to a smaller extent in other seasons, suggesting differential complex spatial-temporal dependency of the WEC.