Atomic‐level control over the position and growth of a single and continuous metal chain is an ambitious goal that often requires complex and costly processes. Herein, we demonstrate that 1Pd‐DNA molecules, comprising a continuous single chain of PdII ions, can be prepared by a simple self‐assembly reaction between the complex [Pd(Cheld)(CH3CN)] (1Pd_CH3CN) (Cheld=chelidamic acid) and single‐stranded DNA homopolymers (ss‐DNA) containing adenine (A) or 7‐deazaadenine (X) bases. The single PdII‐base pairs [1Pd(N1‐A)] and [1Pd(N1‐X)] were synthesized and characterized in solution and solid‐state (X‐ray diffraction) revealing an arrangement similar to that of natural Watson–Crick base pairs. Subsequently, 1Pd‐DNA hybrids were prepared, characterized, and their structures studied by small‐angle X‐ray scattering (SAXS) and ab‐initio calculations. The results indicate that the 1Pd‐DNA structures resemble that of double‐stranded DNA, with one strand being replaced by a supramolecular stack of continuous PdII complexes.