Thiacalix[4]-bis-crown (L¹) and thiacalix[4]-bis-thiacrown (L²) were employed as building blocks for supramolecular complexes. Reaction of L¹ with KClO₄ afforded an endocyclic dipotassium(I) complex [K₂(L¹)](ClO₄)₂∙CH₃CN (1). Its monopotassium(I) complex [K(L¹)][Pt(tht)Cl₅] (2, tht = tetrahydrothiophene) was also isolated from the mixed salts as a first example of symmetrical calix[4]-bis-crowns (see below). In the silver(I) complexations, anion-dependent exocyclic silver(I) coordination polymers (CPs) were isolated (3: perchlorate and 4: nitrate). When silver(I) perchlorate was used, for example, a double-stranded 1D CP {[Ag₂(L¹)(ClO₄)₂]^.CH₂Cl₂}_n (3) was obtained, while silver(I) nitrate afforded {[Ag₂(L¹)(NO₃)₂]^.CH₃OH}_n (4) with a brick-wall type 2D CP structure. Unlike L¹, silver(I) complexations with L² afforded the mole ratio dependent products. Below 0.7 equiv of AgCF₃CO₂, 2D CP {[Ag₂(L²)₃(CF₃CO₂)₂]^.6CHCl₃}_n (5) was isolated. Notably, the use of 1.0 equiv or above amount of AgCF₃CO₂ gave a different 2D CP, {[Ag₄(L²)₃(CF₃CO₂)₄]^.CHCl₃^.toluene^.CH₃OH}_n (6). To monitor the mole ratio dependency, the PXRD analysis has been applied.