Ultrashort laser-induced breakdown spectroscopy was used to detect the emission radiation from the breakdown of surface contaminants by a femtosecond laser pulse. This study focused on the detection of visible to near-infrared radiation signatures from molecular fragments of the nitro (NO(x)) group present in the breakdown plasma, where target chemicals of potassium nitrate (KNO(3)) and sodium nitrate (NaNO(3)) were used. Spectral signatures at a wavelength region around 410 nm were observed for both KNO(3) and NaNO(3), and were identified as the fluorescence transitions of the NO(x)-molecular structures. The signatures obtained were systematically analyzed and studied as functions of laser parameters. It is shown that for laser parameters used in this study, laser pulse durations ≥1 ps were not as effective as shorter pulses in generating these signatures. A visible wavelength NO(x) signature and the extended high-intensity propagation of a femtosecond laser could be advantageous to detecting nitro-group energetic materials at standoff distances.