The vibrational spectra of the aniline-pyrrole complex and the corresponding complex cation have been measured in the region of the NH stretching vibration using a mass-selective IR-UV double-resonance technique. In the spectrum of the neutral complex, there are three absorption bands at 3393, 3364, and 3496 cm(-1), which have been assigned to the symmetric and antisymmetric stretching vibrations of the aniline NH2 group and the NH. stretching vibration of pyrrole, respectively. The positions of the first two bands are close to those found in the aniline dimer and aniline-benzene complexes, suggesting that the neutral aniline-pyrrole complex has a similar parallel configuration. In the spectrum of the complex cation, three absorption bands have been observed at 3293, 3435, and 3498 cm(-1). In this case, the first two bands appeared at the same positions as those of the aniline-benzene cation, which indicates that there is a hydrogen bond between one of the NH bonds of the aniline cation and the.pi-electron system of pyrrole. These structures of the aniline-pyrrole complexes and its cation have been confirmed by ab initio MO calculations.