Under ideal analysis settings, the measurement of emission from laser-induced plasma offers a unique capacity for quantifying the major and minor elements present in any kind of sample. Chemometric techniques are extremely efficient and trustworthy tools for determining the quantities of several components in complicated matrices. For the investigation of environmental reference materials, the viability of laser-induced breakdown spectroscopy (LIBS) in conjunction with multivariate analysis (RMs) was examined. Several (Certified/Standard) References Materials of plant and soil origin were examined using LIBS in the current work, and the presence of Al, Ca, Mg, Fe, K, Mn, and Si was detected in the LIBS spectra of these materials. Using the LIBS spectral data, partial least square regression and partial least square discriminant analysis were used as multivariate statistical techniques for the quantitative study of the constituent elements. To verify the accuracy of the calibration models, the concentrations of the various components in test samples were predicted using the calibration models, and the predicted concentrations were then compared to the certified concentrations. The results of two RMs by LIBS were also compared using the non-destructive analytical technique known as Instrumental Neutron Activation Analysis (INAA), which makes use of high-flux reactor neutrons and high-resolution gamma-ray spectroscopy.