Ray fluorescence spectrometry(XRF) can be used to rapidly determine the total content of calcium in fluorite. However, the calcium carbonate included in total calcium will cause in inaccurate results of calcium fluoride. Moreover, copper, zinc and other non-ferrous metal elements can damage the platinum crucible, so acid treatment is required to remove calcium carbonate and other non-ferrous metals. The residues of different samples after acid treatment are different to the ones before and the ratio of the flux to sample is uncertain, thus the content of calcium fluoride cannot he accurately determined. The sample pretreatment conditions, melting conditions and equipment conditions are described. A method for the accurate determination of calcium fluoride in fluorite by fused XRF has been established, which has less interference, good accuracy and precision, simple operation and improved analysis efficiency.