Photoelectron spectroscopy of CuO2- has been studied at three detachment wavelengths : 532 nm, 355 nm, and 266 nm. Vibrationally resolved spectra for two distinct isomers are observed : the Cu(O-2) complex and the copper dioxide molecule. The Cu(O)(2) complex has an electron affinity (EA) of 1.503(10) eV with a ground state vibrational frequency of 530 (50) cm(-1). Its first electronic excited state is 7400 (300) cm(-1) above the ground state. The Cu(O-2)(-) anion is also observed to undergo photodissociation to Cu-+O-2 at both 532 nm and 355 nm detachment wavelengths. The copper dioxide molecule is found to have a high EA of 3.46 (4) eV. Three low-lying excited states are observed within 1 eV above the ground state. The first two excited states of the copper dioxide molecule both possess a totally symmetric vibrational frequency of 640 (60) cm(-1).