Here we show that ionic self-assembly of simple biological tectons can be used to synthesize stable and highly ordered molecular structures. In particular, nucleotides and charged polypeptides can be assembled to form a complex analogous to DNA under relatively benign conditions. The combination of polylysine and pure dGMP leads to a fourfold ladder structure stabilizing an interior G-quartet structure by four polypeptide scaffolds. Making use of the Watson–Crick GC base pairing motive leads to double-stranded complexes. Interestingly, these complexes show stable DNA-like organization in aqueous solutions, as proven by gel electrophoresis and intercalation experiments.