Understanding the distribution and transportation of phosphorus is vital for the sustainable development of aquatic environmental protection and ecological security. The spatial–temporal distribution of phosphorus fractions in water–sediment phases in river systems and their relationships remain unclear in Southwest China. In this study, the spatial and temporal distribution of phosphorus fractions in water–sediment phases in the Tuojiang River, a primary tributary of the Yangtze River which plays important roles in the economy and ecology of the region, and the relationships among the different phosphorus fractions were analyzed. These fractions were soluble reactive phosphorus (SRP), dissolved organic phosphorus (DOP), and total particulate phosphorus (PP) fractions in water, and exchangeable phosphorus (Ex-P), organic phosphorus (Or-P), phosphorus bound by Fe oxides (Fe-P), authigenic phosphorus (Ca-P), detrital phosphorus (De-P), and refractory phosphorus (Res-P) fractions in sediment. The SPR and Fe-P were the dominant phosphorus fractions in the water and sediment, respectively. The TP content was greater in the lower reaches than in the middle and upper reaches. The average abundances of most phosphorus fractions in water–sediment phases showed significant seasonal variations. The Fe-P, Org-P, and TP in sediments were released to the water interface, resulting in the increase of phosphorus in the overlying water. Redundancy analysis (RDA) indicated that the physicochemical properties of water and sediment have a certain influence on the spatial–temporal distribution of the phosphorus fractions. Principal component analysis (PCA) revealed that the main phosphorus source was anthropogenic activities. These results provide primary data regarding phosphorus fractions and contribute to understanding phosphorus cycling and controlling phosphorus pollution in the Tuojiang River.