Anion photoelectron spectra taken at various photodetachment wavelengths have been obtained for GaX2-, Ga2X-, Ga2X2-, and Ga2X3- (X=P,As). The incorporation of a liquid nitrogen cooled channel in the ion source resulted in substantial vibrational cooling of the cluster anions, resulting in resolved vibrational progressions in the photoelectron spectra of all species except Ga2X2-. Electron affinities, electronic term values, and vibrational frequencies are reported and compared to electronic structure calculations. In addition, similarities and differences between the phosphorus and arsenic-containing isovalent species are discussed.