Unsymmerical calix[4]crowns containing [(O4S)(O-5)] (L-1) and [(O4S2)(O-5)] (L-2) as crown loops were employed as new scaffolds both for complexation studies and for network formation, Reactions of L-1 and L-2 with KI in the presence of CuI afforded a copper(I) iodide cluster linked 1D-type endocyclic dipotassium(I) complex [K-2(L-1)(Cu7I9)](n) (1) and a copper(I) iodide cluster linked 1D-type endocyclic monopotassium(I) complex [KL2 (mu(2)-Cu3I4)](n) (2), respectively. By comparison, the reaction of L-2 with KPF6 in the presence of CuI and HgI2 afforded the 1-D endocyclic potassium(I) complex [K(L-2) (CuHgI4)](n) (3), linked with a CuHgI4 cluster unit. The formation of homo- and heterodinuclear complexes in solution was also confirmed by comparative NMR studies.