Group 3 metal-aniline complexes, M(aniline) (M = Sc, Y, and La), are produced in a pulsed laser-vaporization molecular beam source, identified by photoionization time-of-flight mass spectrometry, and investigated by pulsed-field ionization zero electron kinetic energy (ZEKE) spectroscopy and quantum chemical calculations. Adiabatic ionization energies and several low-frequency vibrational modes are measured for the first time from the ZEKE spectra. Metal binding sites and electronic states are determined by combining the ZEKE measurements with the theoretical calculations. The ionization energies of the complexes decrease down the metal group. An out-of-plane ring deformation mode coupled with an asymmetric metal-carbon stretch is considerably anharmonic. Although aniline has various possible sites for metal coordination, the preferred site is the phenyl ring. The metal binding with the phenyl ring yields syn and anti conformers with the metal atom and amino hydrogens on the same and opposite sides of the ring, respectively. The anti conformer is determined to be the spectral carrier. The ground electronic state of the anti conformer of each neutral complex is a doublet with a metal-based electron configuration of nd(2)(n + 1)s(1), and the ground electronic state of each ion is a singlet with a metal-based electron configuration of nd(2). The formation of the neutral complexes requires the nd(2)(n + 1)s(1) ← nd(1)(n + 1)s(2) electron excitation in the metal atoms.