A series of new cavity-containing molecular receptors, “homothiaisocalixnaphthalenes” containing 2,3-dialkoxy-substituted naphthalene units, have been synthesized, and some of their complexation properties have been investigated. The syntheses of the octaethoxy- and n-octapropoxy-octahomotetrathiaisocalix[4]naphthalenes were accompanied by small amounts of the corresponding higher dodecahomohexathia homologues. All of the macrocycles which were synthesized were highly symmetrical and conformationally flexible. Although these new macrocycles were not effective hosts for C₆₀- and C₇₀-fullerenes or the tetramethylammonium cation, two of them were shown, in a limited study, to effectively bind with Ag⁺ and only modestly with Hg²⁺.