Laser-induced breakdown spectroscopy (LIBS) has been widely used to evaluate the elemental composition (e.g., minerals or metal accumulation) on vegetal tissues. The main objective of this work was to differentiate wheat outer tissues during the grain ablation using LIBS and univariate/multivariate analysis. A high resolution spectrometer and a Nd:YAG laser (532 nm, 5 ns) was first used in order to easily identify atomic wheat emission lines. Then a pulsed excimer laser ArF (193 nm, 15 ns) and a compact fiber optic spectrometer was used to acquire LIBS spectral data from each pulse. Univariate and multivariate analyses (MW2D, PLS-DA) were carried out to provide more in depth information from the LIBS experiment. The number of pulses needed to ablate wheat tissues was successfully predicted by the supervised pattern recognition procedure. LIBS used in conjunction with multivariate analysis could be an interesting technique for rapid structural analysis of vegetal material