Measurement of mass-, energy-, and angle-resolved fragment ions reveals that the β value for C+ with kinetic energy ≥~3 eV is ∼0.9 in the region of the O 1s→2πu excitation and that the β value for O+ with kinetic energy ≥~4 eV varies from -0.23 to -0.57 across the O 1s→2πu resonance. These findings postulate that the CO2 molecule excited to the lower branch of the vibronically split O 1s[-1]2πu excited states deforms into a bent geometry while the molecule excited to the higher branch remains in a linear geometry.