Daunomycin derivatives of pT(DT) and oligodeoxynucleotides were synthesized using reactive zwitter-ionic 4-N,N-dimethylaminopyridine derivatives of the terminal phosphate group. Daunomycin oligodeoxynucleotide analogues form more stable complementary complexes than the corresponding non-modified oligonucleotides. Both one- and two-dimensional (2D NOESY and 2D COSY) NMR spectra of DT were recorded and the proton signals assigned. From the detected cross-relaxation between H6 of thymidine and H1', H2', H2" of the carbohydrate residue of daunomycin it was concluded that, in DMSO, the DT molecule has a rather stable conformation, apparently due to the stacking interaction between the mononucleotide and daunomycin residues.