Femtosecond and nanosecond laser-induced breakdown spectroscopy (LIBS) were used to study trinitrotoluene (TNT) deposited on aluminum substrates. Over the detection wavelength range of 200-785 nm, we have observed emission from CN and C(2) molecules as the marker for the explosive with femtosecond LIBS. In contrast, the signal for nanosecond LIBS of TNT is dominated by emission from the elemental constituents of the explosive. Aluminum emission lines from the substrate are also observed with both femtosecond and nanosecond excitation and indicate the role played by the substrate in the interaction.