Six related organo-chalconium silver(i) coordination complexes, including two examples of rare organotellurium-silver coordination, have been prepared and structurally characterised by X-ray crystallography. The series of 5-bromo-6-(phenylchalcogeno)acenaphthene ligands [Acenap(Br)(EPh)] (Acenap = acenaphthene-5,6-diyl; E = S, Se, Te) were independently treated with silver(i) salts (AgBF(4), AgOTf). In order to keep the number of variables to a minimum, all reactions were carried out using a 1 : 1 ratio of Ag/L and run in dichloromethane. The nature of the donor atoms and the coordinating ability of the respective counter-anion affects the structural architecture of the final silver(i) complex, generating a monomeric dinuclear complex {[(AgBF(4)()(2))(2)] }, monomeric, mononuclear, two-coordinate silver(i) complexes {[AgBF(4)(L)(2)] ( L = ; L = )}, a monomeric three-coordinate silver(i) complex {[AgOTf()(2)] }, a monomeric four-coordinate silver(i) complex {[AgOTf()(3)] } and a 1D extended helical chain polymer {[AgOTf()](n)}. The organic acenaphthene ligands all adopt the same ligation mode with the central silver atom (classical monodentate coordination), which employs a variety of coordination geometries (linear, trigonal planar, see-saw, tetrahedral).