A laboratory experiment was carried out to measure volatilisation fluxes of polychlorinated biphenyls (PCBs) from sewage sludge-amended soils. The most commonly practised methods of applying sludge to agricultural land in the UK, namely, surface application, ploughing in to soil and subsurface injection, were simulated inside glass experimental chambers using an anaerobically digested sludge and a sandy loam soil. Humidified air was blown over the surface of the soil/sludge in the chambers for a period of 32 days, in order to sample a sufficient air volume to detect the volatilising PCBs. The resulting PCB volatilisation fluxes from the different sludge application methods were quantified and compared. Volatilisation fluxes of individual congeners were generally highest for the surface sludge (1-cm depth) application and slightly lower for the plough layer (5-cm depth) application. Fluxes from the subsurface layer of sludge (5-cm depth) were only quantified for the lightest congeners near to the end of the experimental run-time. Results from a multiple regression analysis showed that volatilisation fluxes of PCBs from the surface application are highly dependent on both the sludge concentration and the log of the octanol-air partition coefficient (KOA). A well-known soil volatilisation model, developed by Jury et al., was adapted and used to predict fluxes for the different sludge application methods during the experiment. The model predicted volatilisation fluxes that were reasonably comparable to measured fluxes for some congeners, but for others predicted fluxes that were more than an order of magnitude lower than measured fluxes. The model predicted similar loss kinetics to those observed in the experiment. Possible reasons for the dissimilarity between measured and predicted fluxes include inaccuracies in model input parameters and the fact that the models were not developed for predicting fluxes from sludge-amended soils.