Combined Laser Induced Ignition and Plasma Spectroscopy (LI2PS) has the potential to give the exact local composition of a mixture at the ignition point and at the ignition time. However, as different laser energies are required to ignite a particular mixture as function of space, the typical approach using two power meters to calibrate the plasma spectroscopy measurement is not well suited. Furthermore, LI2PS requires single shot measurements and therefore high accuracy. In this paper, a novel calibration scheme is presented for application of Laser Induced Plasma Spectroscopy (LIPS) to gaseous analyses. Numerical simulations of air spectra are used to show that species emission can be used directly from the broadband spectra to determine the plasma conditions. The ratio of nitrogen emission around 744 nm and around 870 nm is found to be a sensitive indication of temperature in the emission ranging from 700 to 890 nm. Comparisons with experimental spectra show identical tendencies and validate the findings of the simulations. This approach is used in a partially-premixed hydrogen–air burner. First, helium is used instead of hydrogen. After an explanation of timing issue related to LIPS, it is shown that the calibration required depends only on nitrogen excitation and nitrogen–hydrogen ratio, without the need to know the deposited power. Measurements of the fuel distribution as function of injection momentum and spatial localization are reported. To illustrate the use of such a single shot approach, combined laser ignition and plasma spectroscopy is proposed. In this case, the calibration is based on hydrogen excitation and hydrogen–oxygen and hydrogen–nitrogen ratio. Results obtained with LI2PS show that ignition is successful only for high power and relatively high hydrogen concentration compared to the local mean. It is expected that LI2PS will become an important tool when dealing with partially-premixed or diffusion flame ignition.