We present the first reported characterisation by x-ray diffraction and high resolution transmission electron microscopy of metals electrodeposited at the bare and templated liquid/liquid interfaces. Additional structural information is also obtained using ion transfer voltammetry as an in situ characterisation tool. In particular, the metallic deposits are shown to consist of aggregates of discrete nanoparticles, predominantly between 3 and 5nm in diameter. Deposition of platinum at the liquid/liquid interface is reported for the first time, which enables a preliminary comparison to be made between the growth mechanism of this metal and the growth of palladium, previously reported at this interface. © 2004 Elsevier Ltd. All rights reserved.