Crystalline semiconducting sulfide and selenide zeolite analogs were synthesized that possess four-connected, three-dimensional tetrahedral networks built from tetravalent (M4+ = Ge4+ or Sn4+, where M = meta) and trivalent (M3+ = Ga3+ or In3+) cations. Microporous materials were obtained in all four combinations of M4+ and M3+, and some of them were thermally stable up to at least 380 degrees C. These materials exhibit framework topologies with pore size ranging from 12 to 24 tetrahedral atoms, high surface area, high framework charge density and ion exchange capacity, and tunable electronic and optical properties.