The use of plasmonic systems based on metallic nanoparticles (NPs) has been largely used for analytical spectroscopy in the last decades, because it allows extremely high sensitivity and very low limits of detection. In the case of laser-induced breakdown spectroscopy (LIBS), the use of NPs deposited on a solid sample surface enables the interaction of the plasmonic system of metallic NPs with the ablated matter during ns-laser pulse irradiation (nanoparticle enhanced laser-induced breakdown spectroscopy, NELIBS) inducing better atomization and excitation of the sample. NELIBS has been applied in several applications and one of the most interesting one is the analysis of biological samples. This is partly due to that LIBS does not have a high sensitivity in biological samples because of the high ionization energy of matrix elements (C, N, H) that tends to quench the plasma and therefore poor signal-to-noise ratio spectra can only be collected. NELIBS can bypass these inconveniences just by employing a single laser shot for the analysis, due to the advantages mentioned above. In this chapter, a set of examples will clarify the promising advantages of NELIBS with respect to conventional LIBS in the case of biological samples.