A procedure is presented for copper(I)-catalyzed [3+2]cycloaddition of nucleosides and nucleotides in near-quantitative yield. Azido−alkyne cycloaddition was appliedfor the preparation of a range of adenosine dimers andderivatives with versatile functionality, as well as for thesmooth condensation of two oligonucleotide strands. Thedescribed technology may find valuable application in thesynthesis of oligonucleotide dimers and conjugates.