Ordered honeycomb microporous films have previously been fabricated from polymeric macromolecules. We report here the successful fabrication of them from the supramolecular self-assembly of small molecules, alkylated guanosine derivatives. The ribbonlike self-assembly of the guanosines in CHCl3 is found to be the intrinsic structure that forms regular microporous structure via Benard-Maragoni convection. Factors such as substrate, solvents, guanosine concentration, and solvent evaporation temperature are revealed to be able to control the size of the formed micropores, which in turn allows for the wettability of the honeycomb film surface to be modulated. These microporous materials exhibit excellent ability of loading organic dyes that eventually leads to the fabrication of luminescent honeycomb films. As structures of both the small molecules that can assemble and their self-assemblies can be varied and controlled, extended applications of this supramolecular method are expected to lead to microporous films of interesting functions.