The modification of the liquid/liquid interface with solid phases is discussed in this article. Modified interfaces can be formed with molecular assemblies, but here attention is focussed on solid materials such as mesoscopic particles, or microporous and mesoporous membranes. Charge transfer across the modified liquid/liquid interface is considered in particular. The most obvious consequence of the introduction of such modifying components is their effect on the transport to, and the transfer of material across, the liquid/liquid interface, as measured voltammetrically for example. One particularly interesting reaction is interfacial metal deposition, which can also be studied under electrochemical control: the initial formation of metal nuclei at the interface transforms it from the bare, pristine state to a modified state with very different reactivity. Deposition at interfaces between liquids is compared and contrasted with the cases of metal deposition in bulk solution and conventional heterogeneous deposition on conducting solid surfaces. Comparison is also made with work on the assembly of pre-formed micron and nanometre scale solids at the liquid/liquid interface. © the Owner Societies 2006.