Cadmium (Cd) uptake by plants or benthic organisms largely depends on its bioavailability in sediments, so it is necessary to understand Cd bioavailability for determining its ecological risks in riverine sediments. Pore water is easily disturbed during sample collection, indicating that there was a shortage of traditional methods for investigating Cd bioavailability. Here, sediment cores were collected from rivers, after which sequential extraction and diffusive gradients in thin films (DGT) method were employed to determine Cd potential bioavailability in the sediments and pore water. We found that Cd concentrations measured by DGT were lower than that in pore water profiles, and Cd distribution in various fractions changed remarkably. Pearson correlation analysis showed significant positive correlations between Cd concentrations measured by DGT and total Cd concentrations (r2 = 0.76), exchangeable and weak acid soluble fraction (r2 = 0.68), ferromanganese fraction (r2 = 0.72) and bound organic matter or oxidizable fraction (r2 = 0.54). However, the correlation was relatively low between Cd concentrations measured by DGT and that in pore water profiles (r2 = 0.26). These results demonstrated that DGT method could provide more accurate information of Cd bioavailability in sediment profiles than traditional methods.