The wettability of aquifer rocks is a key physical parameter which exerts an important control on the transport, residual trapping, distribution and eventual fate of chlorinated hydrocarbon solvents (CHSs) released into the subsurface. Typically chlorinated solvents are assumed to be non-wetting in water saturated rocks and unconsolidated sediments. However industrially formulated solvent products are often combined with basic additives such as alkylamines to improve their performance; and the mineral surfaces of aquifer rocks and sediments usually possess a range of acid and hydrogen-bonding adsorption sites. The presence of these sites provides a mechanism whereby the basic additives in CHSs can be adsorbed at the solvent phase/solid phase interface. Given the amphiphilic molecular structure of these additives, this may result in changes in the wetting conditions of the solid phase. The aim of this study was therefore to test this conjecture for two classes of additives (alkylamines and quaternary ammonium salts) that are often encountered in industrial solvent formulations. Wettability assessments were made on sandstone cores by means of measurements of spontaneous and forced water drainage and spontaneous and forced water imbibition and through contact angle measurements on a smooth quartz surface. No solvent/additive combination produced solvent wetting conditions, though dodecylamine and octadecylamine significantly reduced the water wetting preference of sandstone which frequently resulted in neutral wetting conditions. The large volume of spontaneous water drainage observed in wettability experiments involving cetyltrimethylammonium bromide and octadecyltrimethylammonium bromide, suggested that the sandstone cores in these tests remained strongly water wetting. However equilibrium static contact angles of around 60 degrees were measured on quartz suggesting that the sandstone surfaces should be close to neutral wetting conditions. This paradox was finally resolved by noting that contact between the solvent mixture and water in the sandstone core resulted in a final solvent phase which had an extremely low interfacial tension. It is therefore suspected that the observed spontaneous drainage of solvent from the core was driven by gravitational and buoyancy forces rather than strong water wetting conditions. Finally it was noted that the mobilisation of iron oxide coatings from the sandstone surface had a considerable influence in reducing the interfacial tension and in the formation and stabilisation of TCE/water emulsions.