In sediments, cadmium (Cd) contamination is an increasingly severe global problem facing environmental protection and human health. The mobility and biological toxicity of Cd are related to its chemical speciation. In this work, the Xihe River in Shenyang, China, was the representative of investigation to study the effect of grain size, pH, organic acids, inorganic anions, and cations on the chemical fractions of Cd in sediments by using the European Community Bureau of Reference (BCR) sequential extraction procedure. The result indicated that fine grains (< 63 μm, 0.57%) presented a relatively higher proportion of the oxidizable fraction Cd in the sediments, while the coarse grains (>250 μm, 78.02%) exhibited the more exchangeable/acid-soluble fraction (78.14 wt.%). The amount of Cd released from the sediment decreased dramatically with the pH from 2-6 and leveled off in the pH range of 8-10. The pH significantly influenced the more mobile fraction (Exchangeable/Acid soluble fraction (F1) and Reducible fraction (F2)), meaning that Cd can be a big-source of danger for the upper water environment. The influence of organic acid on the mobility of Cd in sediments followed the order: ethylenediaminetetraacetate acid (EDTA) > citric acid (CA) > tartaric acid (TA)> oxalic acid (OA). The impact of SO42-, Cl-, CO32- and NO3- was not evident in the release of Cd from the sediment. Besides, Ca(II) and Mg(II) had a major influence on F1 of Cd, and Al(III) and Fe(III) affected various chemical fractions of Cd. The study outcomes provide fundamental knowledge for understanding the mobility and potential ecotoxicological impacts of Cd in sediment.