Our recent work on the detection of explosives by laser-induced breakdown spectroscopy (LIBS) is reviewed in this paper. We have studied the physical mechanism of laser-induced plasma of an organic explosive, TNT. The LIBS spectra of TNT under single-photon excitation are simulated using MATLAB. The variations of the atomic emission lines intensities of carbon, hydrogen, oxygen, and nitrogen versus the plasma temperature are simulated too. We also investigate the time-resolved LIBS spectra of a common inorganic explosive, black powder, in two kinds of surrounding atmospheres, air and argon, and find that the maximum value of the O atomic emission line SBR of black powder occurs at a gate delay of 596 ns. Another focus of our work is on using chemometic methods such as principle component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) to distinguish the organic explosives from organic materials such as plastics. A PLS-DA model for classification is built. TNT and seven types of plastics are chosen as samples to test the model. The experimental results demonstrate that LIBS coupled with the chemometric techniques has the capacity to discriminate organic explosive from plastics.