Surface sediments and sediment cores collected from the Pearl River Estuary (PRE) were analyzed for total mercury (THg) concentrations and speciation using a sequential extraction method. The mobility of Hg in sediments was also assessed using a series of single extraction methods. The surface sediments from the PRE showed slightly elevated levels of Hg, with concentrations ranging from 109 to 453 ng/g. The vertical profile of THg in sediment cores indicated an accelerated input of Hg over the past decades. The organo-chelated and strong-complexed Hg species were the dominant Hg species in the sediments, while the more mobile phases of Hg made up less than 0.5% of THg. Less than 10% of the Hg in the sediments was extracted by single extraction, depending on the extractant employed. Significant relationships were found between the total organic carbon and THg, geochemical speciation, and extractability, indicating the important role of organic matter in controlling the distribution, mobility, and bioavailability of Hg in sediments. © 2012 Elsevier Ltd.