Biomass pellets are a potential renewable and clean energy source. With the advantages of perfect combustion performance and easy storage and transport, biomass pellets have gradually replaced fossil fuels and become widely used. Rapid and accurate determination of biomass pellets’ quality is critical to efficient energy use. Laser-induced breakdown spectroscopy (LIBS) combined with chemometric methods were utilized. The gross calorific value (CV) and ash content (Ash), volatile matter (VM) and fixed carbon (FC) were firstly measured and analyzed. LIBS spectra and their corresponding elements of biomass pellet samples were analyzed. Three quantitative analysis models for quality indexes including partial least-squares regression (PLSR), least squares-support vector machines (LS-SVM), extreme learning machines (ELM) were further built. All models performed well, especially the LS-SVM model which obtained the best determination results, with all R2 values over 0.95. Concurrently, the modeling performance of ash was slightly better than that of the other three quality indexes, which further confirmed the feasibility of using relevant elements to predict biomass quality indexes. The overall results indicated that LIBS coupled with suitable chemometrics could be an alternative promising method to determine quality indexes of biomass pellets and further improve energy utilization by using biomass materials with better quality.