In order to explore the spatiotemporal variation characteristics and driving mechanism of water quality in the Xiangjiang River Basin, the data of 16 water quality parameters at 113 stations over 26 years from 1990 to 2016 in the Xiangjiang River Basin were collected for synthetically assessing the water quality and identifying its main pollutants through the water quality index and other methods. The causal mechanism of water quality, especially the driving effect of water level and land use pattern, was analyzed. The results showed that: ① The overall water quality grade of the Xiangjiang River Basin during the study period was "good." However, the water quality deteriorated first (from 1990 to 2003) and then improved (from 2004 to 2016). The season variation in water quality was not obvious, but the water quality fluctuation of the wet season was larger. The water pollution load of the main stream decreased successively from the middle reaches, downstream reaches, and upstream reaches. The upstream tributaries had the best water quality, whereas areas with poor water quality were mainly distributed at the mouth of the middle and downstream tributaries, especially in areas where multiple tributaries converged. ② Toxic heavy metals had the characteristics of toxicity, persistence, and bioaccumulation. If they exceeded a certain concentration in water, they were difficult to purify, posing great harm to the natural environment and human health. The toxic metal index (CI1) was the leading factor affecting water quality, in which Hg and Cd were the main parameters affecting the overall water quality of the Xiangjiang River Basin. ③ The water level had a positive impact on the water quality of the Xiangjiang River by diluting environmental parameters. Land type had little effect on heavy metal concentration, whereas forest land could improve water quality. Grassland had a negative correlation with permanganate index over a large scale range (≥ 5 km). The increase in water bodies, arable land, and impermeable surface areas within the watershed increased the probability of high fecal coliform concentration in the water body. ④ With the increase in buffer distance, the water quality explained by the land use pattern increased. On the scale of 10 km buffer zone in the riparian zone, the explanation degree by land use pattern on water quality was the highest, which was an effective scale for water quality control of the Xiangjiang River. This research showed that the driving factors of heavy metal pollution and other pollution were different, but their regional differences were all obvious in the Xiangjiang River Basin. Therefore, pollution control should be classified and taken according to local conditions.