Organotins present a toxicological risk to biota in the aquatic environment. Understanding the behaviour of these compounds in sediment is challenging, with sophisticated analytical techniques required for their measurement. We investigated the use of silica-bound sorbents for diffusive gradients in thin-films (DGT) adsorption gels to pre-concentrate five organotins (monobutlytin (MBT), dibutyltin (DBT), tributyltin (TBT), diphenyltin (DPhT), triphenyltin (TPhT)) found frequently in coastal sediment. C8 sorbent showed optimum performance in uptake and recovery of organotins for pH and ionic strength ranges typical of coastal waters. Recoveries from adsorption gels deployed in filtered sea water were MBT = 123 ± 20%, DBT = 75 ± 12%, TBT = 81 ± 16%, DPhT = 72 ± 30%, TPhT = 58 ± 10% respectively. Devices were used to investigate DGT fluxes and pore water concentrations of organotins in coastal sediment collected from a contaminated site. DGT fluxes measured in sediment cores for the five organotins ranged between 4.3 × 10−8 and 1.6 ×10−5 ng cm2 s−1. The depletion of organotin species within pore waters at the interface with DGT devices was measured over a series of deployment times (2, 7, 14, 21 and 28 days) and provided estimates of the concentration of organotins in pore waters at Langstone Harbour, UK, prior to depletion by the DGT device and information on their spatial heterogeneity. The novel in situ DGT device developed can pre-concentrate organotins from pore waters in coastal sediment core samples and allows their detection at low environmental concentrations using conventional gas chromatographic/mass spectrometric instrumentation. Use of the DGT device overcomes many problems associated with the conventional pore water sampling of organotins. Our preliminary data suggests it has potential in the future to be a useful tool in investigating the environmental fate of these pollutants. The use of the C8 gel will also allow for the simultaneous sequestration of other semi- and non-polar analytes present in the pore water.