Chemical composition, an important quality index for perlite, has great influence on the expansion characteristics of perlite. At present, the component analysis of perlite is mainly traditional chemical methods such as capacity, weight, Spectrophotometry and Atomic Absorption Spectrometry. These methods are not only complicated, but it is also impossible to determine the analysis results of all target elements simultaneously. The X-ray Fluorescence Spectrometry (XRF) method for determining major elements of Si, Al, Fe, Ca, Mg, Ti, K and Na in perlite has been established with fusion sampling preparation and is described in this paper. The perlite samples were fused with lithium tetraborate-lithium metaborate (mass ratio of 67:33) as the fusing reagent, the mixed solvent dilution ratio was 1:10 and the fusing temperature was 1050℃. The results show that these experimental conditions satisfy the requirements of analysis and overcome the problem of lower measurement results of silicon due to uneven expansion when fusing perlite samples at high temperature. After the instrument parameters were optimized, working curves were established and the matrix effect was corrected by using various national standard materials and self-made perlite management samples. The determination values obtained by using the XRF method are in good agreement with those measured by traditional chemical methods. The method detection limit is lower than 0.05% and the method precision degree(RSD, n=12) is lower than 1.5%. Compared with classical analysis methods, the XRF method has many advantages such as high efficiency, is environmentally-friendly, has high precision and accuracy, and is simple to conduct. The results show that the major elements in perlite can be determined rapidly and simultaneously by the XRF method with one time fusion sampling preparation.