Images and emission spectra of sparks produced by laser-induced breakdown of methane and propane air mixtures were investigated with a high degree of spatial and temporal resolution. The laser-induced breakdown was generated by focusing a 532-nm nanosecond pulse from a Q-switched Nd:YAG laser. The data were collected using an intensified high-speed camera and a single/multi-fiber Cassegrain optics system coupled to an ICCD spectrometer. Emission spectra of OH ∗, CN ∗, CH ∗, and C ∗ 2 radicals were also collected using spectra boxes. The results provided information about the different stages of the laser-induced breakdown, with a specific focus on the transition from a flame kernel to a self-sustaining flame. The plasma shape and emission spectrum were very reproducible. The differences in the size of the flame kernel and the evolution of the radical emissions were analyzed for mixtures that fired or misfired. The impact of the level of radicals in the flame kernel was a critical parameter for the firing process, starting around 1 μs after the laser-induced breakdown. The transition from plasma cooling to the classical chemical reactions in the combustion zone was analyzed. Even though the flame kernel size was directly linked to the spark energy, this was not a key parameter toward evolution to a self-sustaining flame. The Taylor blast wave theory was used to plot the location of the shock based on the evolution of the flame kernel size. The location was calculated using a laser-supported detonation model. A very good correlation was observed with the hot gas ignition process. Our results allowed us to obtain information about the process leading to firing or misfiring for similar environments, resulting in a better understanding of the laser breakdown phenomena and the means of utilizing this technique in an industrial context.