We have demonstrated a two-step laser-enhanced ionization (LEI) technique to be potentially useful in measuring a spatially resolved temperature in an atmospheric air/acetylene flame. As a complement to the existing optical methods, LEI detection shares the advantages of extremely high sensitivity and the capability of achieving a high spatial resolution, confined to the dual-beam intersection area of 1 mm × 1 mm. A theoretical model was developed to precisely extract the temperature information from the obtained two-step LEI signal. The physical parameters required in the experiment include simply the relative values of the LEI signals, associated with the fine-structure doublets of a selected thermometric species, and their corresponding laser energies. The subsequent treatment is also convenient without the need to know the absolute energy of the incident laser beam and to accurately calibrate the detection system. Al and Ga were selected as the thermometric species. The resultant radial and axial temperature mappings are consistent with each other and are also comparable with those reported by other optical methods.