Direct excitation luminescence spectroscopy is used to monitor binding of Eu(III) to oligodeoxyribonucleotides in solution. The position of the⁷F_o to ⁵D_o excitation peak of Eu(III) is used in conjunction with luminescence lifetime studies to monitor binding and dehydration of the Eu(III) ion in the presence of DNA. Our studies show that only a limited number of structures including certain hairpin loops, nucleobase mismatches and internal loops bind to Eu(III) to produce a red-shifted excitation peak with concomitant dehydration of the Eu(III) ion. Prospects for the detection of these structures by examination of signature changes in the excitation spectra and luminescence lifetime of the bound Eu(III) ion will be discussed.