Spatio-temporal distribution and leachability of some trace elements (TE) were investigated in sediments of the Xiangjiang River, tributary of the Yangtze River. Based on data collected during 2015–2017, a literature review and geoaccumulation indexes, the pollution level was the highest for Cd, Sb and Hg (Igeo > 3). Over the period reviewed, the TE contamination level displayed almost no temporal variation but an obvious spatial distribution. The most upstream contamination hotspot (Cd > Cr > As, Cu, Pb, Zn > Hg, Sb) was the Songbai section. This hotspot did not spread further downstream. The second hotspot identified was the Zhuzhou–Xiangtan section, impacted by Cd > Hg, Pb, Zn > Cu, with the Zhuzhou area being particularly highly impacted by Pb and Zn. A 30-day leaching experimental protocol under aerobic and anaerobic conditions was carried out to access TE mobility. Low percentages of TE released were calculated, showing that the TE fate mostly depends on the stability of bearing phases under specific physicochemical and microbial conditions. In this case, the studied sediments can be an important sink for these TE. However, some environmental issues have to be considered as some leachate concentrations of contaminants (As, Cr, Cu and U) released into water exceed freshwater aquatic life criteria.