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Systematic Ce anomalies for whole-rock have been obtained from the shale-dominated, continuous, and pelagic sedimentary sequences spanning the Ordovician/Silurian (O/S) boundary at the Tieshui (铁水) of Xiushan (秀山), Chongqing (重庆), South China. Ce anomalies across the O/S boundary are recognized in three intervals, Wufeng (五峰), Guanyinqiao (观音桥) and Longmaxi (龙马溪). The calculated Ce/Ce* values of Wufeng Formation range from 0.84 to 0.96 (avg. 0.90). In the Guanyinqiao Formation, the values of calculated Ce/Ce* range from 0.73 to 0.85 (avg. 0.79). The Ce/Ce* values of uppermost Longmaxi Formation range from 0.87 to 0.96 (avg. 0.91). All along the section, the magnitude of the Ce anomaly is always negative, but is more significant in the Guanyinqiao Formation. The relatively higher Ce/Ce* values in the Wufeng and Longmaxi shales are likely to be due to the sediments deposited under rather reducing conditions. The Ce anomaly apparently does play some regular roles in the anoxic events that accompany prominent mass extinctions, and this work provides new data of critical importance for constraining models on the end-Ordovician anoxic events and mass extinctions.