Quantitative emission spectroscopy has been used to study the plume formed following laser ablation of YBCO in an oxygen atmosphere. Excited state population distributions, determined from emission line intensity ratios, are used to investigate spatiotemporal variations in the local Boltzmann temperatures for both neutral and ionic species within the expanding plume. Temperatures, obtained from emission line intensity ratios of both Cu(I) and Y(I), decrease slowly and nonadiabatically in the range 1.0–0.5 eV during plume expansion. Higher initial Boltzmann temperatures of ∼3 eV are however obtained from the emission line intensity ratios of fast ions, which dominate the composition of the highly luminous expanding front of the plume. Quantitative comparison of emission intensities for the different neutral species present indicate that the neutral composition in the luminous region of the expanding plume is increasingly dominated by Cu(I) which has a faster expansion velocity and lower oxidation rate than Y(I) and Ba(I). ©1995 American Institute of Physics.