A series of complex networks have been synthesized from the association of potassium and rubidium p-halide-substituted aryloxides using 1,4-dioxane molecules as neutral linkers. The crystalline polymers [(4-F-C6H4OK)(6)center dot (dioxane)(4)](infinity) (1), [(4-I-C6H4OK)(6)center dot(dioxane)(6)](infinity) (2), and [(4-I-C6H4ORb)(6)center dot(dioxane)(6)](infinity) (3) are built from discreet, hexameric M6O6 aggregates. Compound 1 forms an unusual 16-connected framework involving both K-F and K-O-diox interactions. Each hexamer connects to eight neighboring aggregates through double-bridging contacts, resulting in a body-centered cubic (bcu) topology. Compounds 2 and 3 are isostructural, 12-connected networks, where each aggregate utilizes six dioxane double bridges to form primitive cubic (pcu) nets. In contrast, the complexes [(4-Cl-C6H4OK)(3)center dot(dioxane)](infinity) (4), [(4-Br-C6H4OK)(2)center dot (dioxane)(0.5)](infinity) (5), and [(4-Br-C6H4ORb)(5)center dot(dioxane)(5)](infinity) (6) are built from one-dimensional (1D) inorganic rods composed solely of M-O-Ar, interactions. The extended structures of both 4 and 5 can be described as pcu nets, where parallel 1D inorganic pillars are connected through dioxane bridges. Compound 6 is also composed of parallel 1D inorganic rods, but in this instance the coordinated dioxane molecules do not bridge, resulting in isolated, close-packed chains in the solid state.