In this paper, an acetone planar laser-induced fluorescence (PLIF) technique for nonintrusive temperature imaging is demonstrated in gas-phase (Pr = 0.72) turbulent Rayleigh–Bénard convection at Rayleigh number Ra = 1.3×105. The PLIF technique provides quantitative spatially correlated temperature data without the flow intrusion or time lag associated with physical probes, and without the significant path averaging that plagues most optical heat-transfer diagnostic tools, such as the Mach–Zehnder interferometer, thus making PLIF an attractive choice for quantitative thermal imaging in easily perturbed, complex three-dimensional flow fields. The "instantaneous" (20-ns integration time) thermal images presented have a spatial resolution of 176×176×500 µm and a single-pulse temperature measurement precision of ± 2.5 K, or 2.5% of the total temperature difference. These images represent a two-dimensional slice through a complex three-dimensional flow, allowing for thermal structure of the turbulence to be quantified. Statistics such as the horizontally averaged temperature profile, root-mean square (rms) temperature fluctuation, two-point spatial correlations, and conditionally averaged plume structures are computed from an ensemble of 100 temperature images. The profiles of the mean temperature and rms temperature fluctuation are in good agreement with previously published data, and the results obtained from the two-point spatial correlations and conditionally averaged temperature fields show the importance of large-scale coherent structures in this turbulent flow.