The present study focuses on the laser-induced breakdown spectroscopy (LIBS) studies on different parts of tooth samples. The hardness of different parts of tooth samples belonging to different age groups has been studied using ionic-to-atomic intensity ratio of Ca spectral line. From this ratio, we infer that enamel is the hardest part of teeth. The principal component analysis (PCA) on LIBS data of different parts of teeth gives PC1 (96%) and PC2 (4%), which explains maximum variance present in data set. Therefore, this work demonstrates the suitability of LIBS along with PCA for routine in vitro/in vivo dental practices.