Ultraviolet–Visible emission from iso-octane combustion was measured behind reflected shock waves. OH ∗ , CH ∗ and C 2 ∗ were recorded as the major intermediate species. When the equivalence ratio increases, the emission intensity ratio of OH ∗ /CH ∗ decreases and that of C 2 ∗ /OH ∗ increases. Rotational and vibrational temperatures were determined by comparing the measured emission spectra with the simulated ones of CH ∗ and C 2 ∗ . The rotational temperatures are in good agreement with the calculated adiabatic flame temperatures and the vibrational temperatures are significantly higher. Furthermore, ignition delay times were obtained to provide a database for the validation of the kinetic mechanism.