Aluminum-trimethylphosphine and trimethylarsine have been prepared by pulsed laser vaporization. Their electronic spectra have been obtained for the first time, using pulsed field ionization zero electron kinetic energy (ZEKE) photoelectron spectroscopy. The ZEKE spectra reveal the information about adiabatic ionization energies, intermolecular and ligand vibrations, and charge effects on molecular geometries. In coordination with the experimental measurements, density functional theory has been used to calculate equilibrium geometries, vibrational frequencies, and bond dissociation energies for the neutral and ionic complexes. The calculations predict that ionization causes the most significant geometry changes in the Al-P-C or Al-As-C angles, in agreement with the experimental observations. The aluminum ion and atom bind phosphorus more strongly than arsenic in these species.