The GaO and GaO2 molecules were investigated using negative ion photoelectron spectroscopy. All the photoelectron spectra showed vibrationally resolved progressions. With the aid of electronic structure calculations and Franck–Condon spectral simulations, different molecular parameters and energetics of GaO-/GaO and GaO2-/GaO2 were determined, including the electron affinity of GaO, the vibrational frequency of GaO-, and the term energy, spin-orbit splitting, and vibrational frequency for the first excited A 2ΠΩ state of GaO. The GaO2- photoelectron spectra comprised three bands assigned as transitions from the linear X 1Σg+ ground state of GaO2- to three linear neutral states: the A 2Πg, B 2Πu, and C 2Σu+ states. The symmetric stretch frequencies of the anion and three neutral states as well as the spin-orbit splitting of the neutral 2Π states were determined. Electronic structure calculations found the neutral lowest energy linear structure to be only 63 meV higher than the neutral bent geometry. [ABSTRACT FROM AUTHOR]