Femtosecond laser ablation was investigated for direct solid sample chemical analysis. The phonon relaxation time in a solid is of the order of 100 fs, which is the same as the laser pulse duration. For such excitation, there should be little time for the matrix to experience a “temperature” during the laser pulse. If the surface explodes before the photon energy is dissipated as heat in the lattice, the ablation process should produce stoichiometric vapor (elemental fractionation should be negligible). Based on this hypothesis, NIST glasses were ablated using 100 fs laser pulses at 800 nm, with subsequent elemental analysis using the ICP-MS. Pb and U intensities, and Pb/U ratios in the ICP, were measured during repetitively femtosecond-pulsed ablation. These data show that fluence (laser energy/spot area) has a significant influence on the amount of mass ablated and on the degree of fractionation. An optimal fluence was found at which the fractionation index approached unity; negligible fractionation. Infrared femtosecond laser ablation produced similar characteristics to UV nanosecond laser ablation.