Abstract A detailed understanding of transport phenomena and reactions in near-wall boundary layers of combustion chambers is essential for further reducing pollutant emissions and improving thermal efficiencies of internal combustion engines. In a model experiment, the potential of laser-induced fluorescence (LIF) was investigated for measurements inside the boundary layer connected to flame-wall interaction at atmospheric pressure. Temperature and species distributions were measured in the quenching boundary layer formed close to a cooled metal surface located parallel to the flow of a premixed methane/air flat flame. Multi-line NO-LIF thermometry provided gas-phase temperature distributions. In addition, flame species OH, CH2O and CO were monitored by single-photon (OH, CH2O) and twophoton (CO) excitation LIF, respectively. The temperature dependence of the OH-LIF signal intensities was corrected for using the measured gas-phase temperature distributions. The spatial line-pair resolution of the imaging system was 22 lm determined by imaging microscopic line pairs printed on a resolution target. The experimental results show the expected flame quenching behavior in the boundary layer and they reveal the potential and limitations of the applied diagnostics techniques. Limitations in spatial resolution are attributed to refraction of fluorescence radiation propagating through steep temperature gradients in the boundary layer. For the present experimental arrangements, the applied diagnostics techniques are applicable as close to the wall as 200 lm with measurement precision then exceeding the 15– 25% limit for species detection, with estimates of double this value for the case of H2CO due to the unknown effect of the Boltzmann fraction corrections not included in the data evaluation process. Temperature measurements are believed to be accurate within 50 K in the near-wall zone, which amounts to roughly 10% at the lower temperatures encountered in this region of the flames.