The effect of the shape of the nanoparticles on the nanoparticle-enhanced LIBS (NELIBS) signal should be clarified. The present study reports on the effect of the silver (silver chloride) nanoparticle shape (nanospheres, nanocubes, and nanowires) on the LIBS signal for different target materials; two metals (aluminum and zinc) and one semiconductor (silicon). The shape enhancement factor and the plasma parameters, namely plasma temperature and electron density, have also been evaluated. Silver nanoparticles have been characterized using different techniques, including SEM, UV-vis, and XRD. The results showed that the clusters formed in the silver nanowires and nanocubes play an essential role in the laser pulse's absorption mechanism and, consequently, enhance the LIBS signal. Nanowires followed by nanocubes showed better enhancement than nanospheres, confirmed by the shape-dependent enhancement factor. However, the laser-induced plasma parameters (plasma temperature and electron density) have not been affected much by the nano-shape change.