Slow diffusion of Cu(ClO4)2 with p-C6H4(SiMe2(4-Py))2 yields a supramolecular framework consisting of two kinds of channels via self-assembly of a 1D double-stranded chain in a prismatic fashion. The channel has a 11 x 11 A2 cross section (Cu...C = 11.13 A) with a 6 x 6 A2 square pore. The channels are infinitely arranged, resulting in another kind of channel with similar pores. Thus, two different kinds of channels with different solvate molecules coexist in a 1:2 ratio. Weak C-H...pi interaction may be one of the driving forces in the assembly of the prismatic channel structure.