A crystalline nanoporous molecular network was tailored by supramolecular assembly of pentacene and F16CuPc on Cu(100). The structure and self-assembly mechanisms of the pure and binary layers were analyzed by STM. F16CuPc films and mixed layers of pentacene/F16CuPc in a ratio of 2:1 show two enantiomorphic chiral domains with high structural order in contrast to pentacene which exhibits no long-range order in pure films. A model of the epitaxial relationship on Cu(100) is given, which suggests C-F...H bonding as a possible driving force for the bimolecular self-assembly in addition to the still strong interaction between the substrate and the organic bilayer.