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Rivers are an important source of water in humid regions, but their availability is greatly limited by water chemistry. In order to accurately identify the changes in river water chemical composition, the compositional analysis method (CoDA) is proposed from the perspective of compositional data analysis theory, which considers the geochemical riverine system as a whole and detects the compositional changes of the entire watershed. The basic data analysis is carried out by traditional analysis methods, and the results show that the hydrochemical characteristics of different sections of the basin have significant features. The water chemistry of Dongxi River is of the HCO3− Ca type. The water of the Xixi River shows a gradual evolution from the HCO3-Ca type and high SO42− content in the upper reaches to the Cl-Ca type in the lower reaches. The hydrochemistry of river water in the watershed is mainly affected by rock weathering leaching (PC1) and agricultural and domestic pollutant discharge (PC2), with a contribution rate of 48.4% and 19.7%, respectively. Rock weathering, mining, and agricultural pollution are the main factors affecting the chemical composition of river water in different regions. The spatial composition of a single sample at different scales is monitored by the Mahalanobis distance approach in an iterative manner to minimize the influence of a single anomaly on the composition center. The results show that the main reasons for the change in river water chemical composition along the Xixi River are attributed to mine pollution, domestic pollution, and tea plantation and that along the Dongxi River is caused by domestic pollution. The hydrochemical composition changes after the confluence of the Xixi River and Dongxi River are mainly affected by human activities and seawater in urban areas. This research could provide new perspectives and methods for detecting the influences of human and natural factors on the hydrochemistry of river water in humid regions worldwide. [ABSTRACT FROM AUTHOR]