Femtosecond laser time-of-flight mass spectra of solid samples of trinitrobenzene (TNB), trinitrotoluene (TNT) and trinitrophenol (TNP) have been recorded. Desorption of the solid samples was enacted by the fourth harmonic output (266 nm) of a 5 ns Nd:YAG laser. Subsequent femtosecond post-ionisation of the plume of neutral molecules was achieved using 800 nm laser pulses of 80 fs duration. Mass spectra have been recorded for desorption laser intensities from 2-6 × 109 W cm-2 with ionisation laser intensities between 2 × 1014 and 6 × 1015 W cm-2. Femtosecond laser ionisation has been shown to be capable of generating precursor and characteristic high-mass fragment ions for labile nitro-aromatic molecules commonly used in high-explosive mate...