The He I UV photoelectron spectra of both digallane, Ga2H6, and gallaborane, GaBH6, have been recorded for the first time, affording ionization energies in good agreement with calculated values. Comparisons are made between the photoelectron spectra of Ga2H6, GaBH6, and the previously studied B2H6 One band for each molecule is sufficiently well-resolved to reveal a vibrational progression in one or more totally symmetric M-H-t stretching modes (M = Ga or B; t = terminal) of the molecular ion : this assignment is confirmed for digallane by studies on Ga2D6.