Owing to the exceedingly small mass involved, complete elemental characterization of single nanoparticles demands a highly precise control of signal background and noise sources. LIBS has demonstrated remarkable merits for this task, providing a unique tool for the multielemental analysis of particles on the attogram-picogram mass scale. Despite this outstanding sensitivity, the air plasma acting as a heat source for particle dissociation and excitation is a meddling agent, often limiting the acquisition of an accurate sample signature. Although thermal effects associated with ultrashort laser pulses are known to be reduced when compared to the widely used nanosecond pulse duration regime, attempts to improve nanoinspection performance using ultrafast excitation have remained largely unexplored. Herein, picosecond laser pulses are used as a plasma excitation source for the elemental characterization of single nanoparticles isolated within optical traps in air at atmospheric pressure. Results for picosecond excitation of copper particles lead to a mass detection limit of 27 attogram, equivalent to single particles 18 nm in diameter. Temporally and wavelength-resolved plasma imaging reveals unique traits in the mechanism of atomic excitation in the picosecond regime, leading to a deeper understanding of the interactions occurring in single nanoparticle spectroscopy.