A new technique, IR-IR-UV hole-burning, is reported for obtaining conformation specific IR spectra when the electronic spectra are too closely overlapped to obtain clean spectra free from interference from other conformations via standard ion dip or fluorescence dip methods. The 4'-aminobenzo-15-crown-5 ether-(HDO) complex is used as an example, on which the method was applied to prove the presence of two conformations having overlapped electronic spectra and to assign IR transitions belonging to the same conformation.