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This paper presents pulsed-field ionization, zero electron kinetic energy (ZEKE) photoelectron and threshold photoionization spectra of M-X(CH3)3 (M = Ga, In; X = P, As). The ZEKE spectra exhibit well-resolved vibrational structures. A comparison with B3LYP calculations shows that the spectrum of In-P(CH3)3 arises from the 1A1 ← 2E transition and the spectra of Ga-P(CH3)3 and Ga-As(CH3)3 arise from transitions of a Jahn–Teller distorted doublet state to the 1A1 state. The intensities of the 1A1–2E transition in the indium species are described with the Franck–Condon approximation, while the transitions in the gallium complexes are more complicated due to the dynamic Jahn–Teller effect. The adiabatic ionization potentials of Ga-P(CH3)3, In-P(CH3)3, and Ga-As(CH3)3 are 39 635, 38 930, and 40 322 cm–1, respectively, and the ionization threshold of In-As(CH3)3 is ~39 550 cm–1. The metal–ligand stretching frequencies are 143, 116, and 125 cm–1 for Ga+-P, In+-P, and Ga+-As, respectively, and 96 cm–1 for In-P. The intermolecular bending frequencies are 71, 65, and 42 cm–1 for Ga+-P-C, In+-P-C, and Ga+-As-C, respectively, and 47 cm–1 for In-P-C. In addition, ligand-based vibrational frequencies are determined for the CH3 wag, PC3 and AsC3 umbrella, and P-C stretching vibrations. [ABSTRACT FROM AUTHOR]