The two-dimensional self-assembly of a nonsymmetric adenine DNA base mixed with symmetric perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules is investigated using scanning tunneling microscopy (STM). We experimentally observe that these two building blocks form a complex close-packed chiral supramolecular network on Au(111). The unit cell of the adenine?PTCDA nanoarchitecture is composed of 14 molecules. The high stability of this structure relies on PTCDA?PTCDA and PTCDA?adenine hydrogen bonding. Detailed theoretical analysis based on the density functional theory (DFT) calculations reveals that adenine molecules work as a ?glue?, providing additional strengthening to the PTCDA-based skeleton of this sophisticated multicomponent nanoarchitecture. At the same time, we find that orientation and chirality of adenine molecules across the monolayer is likely to vary, leading to a disorder in the atomistic structure of the entire assembly. The two-dimensional self-assembly of a nonsymmetric adenine DNA base mixed with symmetric perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules is investigated using scanning tunneling microscopy (STM). We experimentally observe that these two building blocks form a complex close-packed chiral supramolecular network on Au(111). The unit cell of the adenine?PTCDA nanoarchitecture is composed of 14 molecules. The high stability of this structure relies on PTCDA?PTCDA and PTCDA?adenine hydrogen bonding. Detailed theoretical analysis based on the density functional theory (DFT) calculations reveals that adenine molecules work as a ?glue?, providing additional strengthening to the PTCDA-based skeleton of this sophisticated multicomponent nanoarchitecture. At the same time, we find that orientation and chirality of adenine molecules across the monolayer is likely to vary, leading to a disorder in the atomistic structure of the entire assembly.