A tripodal system L, in which urea fragments are appended to the three terminal amine nitrogen atoms of a tris(2-aminoethyl)amine (tren) subunit, includes a CuII ion and two anions X-, according to a cascade mechanism through three well defined stepwise equilibria in a DMSO solution. The first anion X- (halide, N3-, NCS-, NO2 -, H2PO4-) seeks the CuII centre coordinated by the tren moiety; the second anion X- interacts with the trisurea cavity, but this occurs only if the stronger H-bond acceptors, such as N3- and H2PO4-, are used. Binding of the second X- ion is favoured by the preorganising effect exerted by the metal and disfavoured by the steric and electrostatic repulsions between the anions. Under the appropriate conditions, heterodinuclear complexes of formula [CuII(L)(Cl)(H2PO4)] can be obtained in solution, in which Cl- is bound to the metal centre and H2PO4- interacts with the trisurea compartment.