The outstanding self-recognition properties of DNA have been exploited in the use of this biomolecule as a template for the construction of nanoscale assemblies [1] and hybrid structures. [2,3] To further expand the utility of DNA for other applications, research is currently aimed at increasing its intrinsically low electric conductivity.[4] The selective coating of DNA with a thin layer of a conductive element, such as Ag, [5] Pd, [6] Pt, [7] Cu, [8] or Co, [9] has emerged as a promising avenue. Most coating procedures involve the reduction of electrostatically bound metal ions on the DNA by an exogeneous reductant to give small metal clusters attached to the DNA. In a second, development step, known from black-andwhite photography, these metal clusters function as nucleation sites for the reductive deposition of metal atoms until a continuous conductive coating is formed. Novel procedures aimed at increasing the selectivity of the metallization process are the decoration of DNA with functional groups to control the spatial distribution of the nucleation sites, [10] the photochemical deposition of silver on DNA strands, [11] and the formation of DNA-Pt II adducts as precursors for metal deposition on DNA.[12] The most critical step in the whole metallization process is the initial nucleation step. The uniformity and the distribution of the metal clusters define the homogeneity of the development step and hence the result of the metallization process. Unfortunately, nucleation in chemical reactions is still a poorly understood process and is therefore difficult to control.To coat DNA with silver, small silver clusters Ag n (n = 2, 4, 6…) that are able to undergo a development process need to be deposited on the DNA. These clusters can be formed in a redox reaction between Ag + in solution and aldehyde groups present on the DNA (Tollens reaction). Owing to the stoichiometry of the redox process, one aldehyde group can reduce two silver ions to form an Ag 2 cluster. Dialdehyde groups should be able to form an Ag 4 cluster (Scheme 1). It is suspected that these Ag 4 clusters, as a result of their electronic structure, are the smallest stable, developable (magic-size) silver clusters.[13] If this hypothesis is correct, the controlled formation of Ag 4 clusters on DNA should enable more reliable DNA metallization.To construct DNA with dialdehyde moieties, we functionalized DNA with cis-3,4-dihydroxypyrrolidine units, which Scheme 1. Transformation of diol-modified DNA-1 and DNA-3 into aldehyde-and dialdehyde-modified DNA-2 and DNA-4, followed by metallization steps.