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 L1–L3 [Acenap(Br)(EPh)] (Acenap = acenaphthene-5,6-diyl; E = S, Se, Te) were independently treated with silver(I) salts (AgBF4, 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 {[(AgBF4(L1)2)2] 1}, monomeric, mononuclear, two-coordinate silver(I) complexes {[AgBF4(L)2] (2 L = L2; 3 L = L3)}, a monomeric three-coordinate silver(I) complex {[AgOTf(L2)2] 5}, a monomeric four-coordinate silver(I) complex {[AgOTf(L1)3] 4} and a 1D extended helical chain polymer {[AgOTf(L3)]n6}. The organic acenaphthene ligands L1–L3 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).