The vibrational frequencies of the N-H stretching modes of aniline, after forming a strong H-bonded complex with diethyl ether (DEE), are measured with infrared depletion spectroscopy that: uses cluster-size-selective REMPI time-of-flight mass spectrometry. Two strong absorption features observed at 3372 and 3478 cm(-1) are assigned to the H-bonded and free N-H stretching vibrations of the 1:1 aniline-DEE complex. The spectral broadening observed for the free and H-bonded N-H stretching modes indicates mode-specific vibrational energy dynamics. While the narrow bandwidth (approximate to 3 cm(-1)) of the N-H stretch at 3478 cm(-1) incorporates all the common broadening mechanisms including IVR, the broader (approximate to 10 cm(-1)) absorption feature at 3372 cm(-1) suggests vibrational predissociation/IVR of the H-bonded complex, with a subpicosecond lifetime. The red shifts of the N-H stretching vibrations of aniline agree with the ab initio calculated (MP2/6-31G**) aniline-DEE structure in which one of the N-H bonds of aniline interacts with the oxygen atom of DEE through a hydrogen bond, giving a binding energy of 13 kJ mol(-1) with due corrections for BSSE and zero-point energy. The electronic 0-0 band origin for the S-1 <- S-0 transition is observed at 33292 cm(-1) giving a significant red shift of 737 cm(-1) from that of the bare aniline. The vibrational bands associated with the R2PI spectrum are assigned to the intermolecular modes of the complex.