Many sediment quality assessment frameworks incorporate contaminant bioavailability as a critical factor regulating toxicity in aquatic ecosystems. However, current approaches do not always adequately predict metal bioavailability to organisms living in the oxidised sediment surface layers. The deployment of the diffusive gradients in thin films (DGT) probes in sediments allows labile metals present in pore waters and weakly-bound to the particulate phase to be assessed in a time-integrated manner in situ. In this study, relationships between DGT-labile metal fluxes within 5 mm of the sediment-water interface and lethal and sub-lethal effects to the amphipod Melita plumulosa were assessed in a range of contaminated estuarine sediments during 10-day laboratory-based bioassays. To account for differing toxicities of metals, DGT fluxes were normalised to water (WQG) or sediment quality guidelines or toxicity thresholds specific for the amphipod. The better dose-response relationships appeared to be the one based on WQG-normalized DGT fluxes, which successfully predicted toxicity despite the wide range of metals and large variations in sediment properties. The study indicated that the labile fraction of metals measured by DGT is useful for predicting metal toxicity to benthic invertebrates, supporting the applicability of this technique as a rapid monitoring tool for sediments quality assessments.