The use of copper(I) in metal-organic assemblies leads readily to the formation of simple grids and helicates, whereas higher-order structures require complex ligand designs. Here, we report the clean and selective syntheses of two complex and structurally distinct CuI12L8 frameworks, 1 and 2, which assemble from the same simple triaminotriptycene subcomponent and a formylpyridine around the CuI templates. Both represent new structure types. In T-symmetric 1, the copper(I) centers describe a pair of octahedra with a common center but whose vertices are offset from each other, whereas in D3-symmetric 2, the metal ions form a distorted hexagonal prism. The syntheses of these architectures illustrate how more intricate CuI-based complexes can be prepared via subcomponent self-assembly than has been possible to date through consideration of the interplay between the subcomponent geometry and solvent and electronic effects.