A new series of azide‐functionalized ruthenium complexes were synthesized. Six trisbipyridine ruthenium complexes bearing one to six azide functions were developed from the corresponding carboxy derivatives. By using four alkyne‐functionalized DNA sequences and performing copper‐catalyzed azide–alkyne cycloaddition (CuAAC) click chemistry reactions, the formation of symmetric and unsymmetric multivalent DNA–ruthenium conjugates was realized. They are composed of one to six oligonucleotides.