Laser-induced breakdown spectroscopy of CO 2 plasma, initially at room temperature and pressures ranging from 6.4 to 101kPa was investigated using a transverse excitation atmospheric CO 2 pulsed laser (λ=10.532μm, a full width at half maximum of 64ns, and an intensity from 1.2 to 5.6GWcm −2 ). The strong emission of the CO 2 plasma shows excited neutral O and C atoms and ionized O + and C + species. The medium-weak emission is due to electronic relaxation of excited species C 2+ , O 2+ , N + , N, H and molecular band systems of C 2 (E 1 Σ g + –A 1 Π u ; e 3 Π g –a 3 Π u ; d 3 Π g –a 3 Π u ), CN(B 2 Σ + –X 2 Σ + ; A 2 Π–X 2 Σ + ), O 2 (b 1 Σ g + –X 3 Σ g − ), O 2 + (A 2 Π u –X 2 Π g ), N 2 (C 3 Π u –B 3 Π g ) and N 2 + (B 2 Σ u + –X 2 Σ g + ). The characteristics of the spectral emission intensities from different species have been investigated as a function of the laser irradiance and CO 2 pressure. Optical breakdown threshold intensities and plasma temperatures were obtained. The evolution of the luminous plasma was examined by time-resolved optical emission spectroscopy. The velocity distributions for different species were obtained from time-of-flight (TOF) measurements. Electron density in the laser-induced plasma was estimated from the Stark broadening method. The temporal evolution of the intensities in the TOF profiles for O + , O 2+ , C, C + and C 2+ species has been used for the estimation of the corresponding three-body electron–ion recombination rate constants.