The oligonucleotide d(TX)9, which consists of an octadecamer sequence with alternating non‐canonical 7‐deazaadenine (X) and canonical thymine (T) as the nucleobases, was synthesized and shown to hybridize into double‐stranded DNA through the formation of hydrogen‐bonded Watson–Crick base pairs. dsDNA with metal‐mediated base pairs was then obtained by selectively replacing W‐C hydrogen bonds by coordination bonds to central silver(I) ions. The oligonucleotide I adopts a duplex structure in the absence of Ag+ ions, and its stability is significantly enhanced in the presence of Ag+ ions while its double‐helix structure is retained. Temperature‐dependent UV spectroscopy, circular dichroism spectroscopy, and ESI mass spectrometry were used to confirm the selective formation of the silver(I)‐mediated base pairs. This strategy could become useful for preparing stable metallo‐DNA‐based nanostructures. Substitution of the original hydrogen bonds by silver(I) coordination bonds in a double‐stranded oligonucleotide comprising Watson–Crick‐paired 7‐deazaadenine and thymine nucleobases leads to a sequential array of metal‐mediated base pairs. The stability of the silver‐containing structure was significantly higher than that of the parent compound while the double‐helix structure was retained.