The novel N,N-diethyl-N′-camphanyl thiourea has been synthesised and characterised by conventional methods. It has been found by means of competitive three-phase transport and competitive two-phase extraction studies to show very high and selective Ag(I) transport and extraction in the presence of Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) using the pH gradient method. A crystal structure suggests that a complex Ag2[(HL-S)(L-μ-S,O)]2 exists, where both monodentate and bidentate modes of coordination are involved.