A new setup for spatially resolved laser-induced breakdown spectroscopy (SR-LIBS) is used for the first time to analyze methane-air diffusion flames. Using this configuration, background continuum emission is reduced, signal-to-background noise ratio is increased up to eight times, and spatial resolution is enhanced. The local equivalence ratio is also quantitatively estimated and the width of the secondary combustion region at a specified height above the burner is determined for two different methane flow rates. Furthermore, the threshold energy for spark formation is measured for regions inside and outside the flame. The results show that threshold energy is larger at the secondary combustion region, near the border of the flame, than inside the flame.