An additional photodetector array BLPP-369 was installed on a «Grand-Potok» complex for rapid atomic-emission determination of the fluorine concentration in fluorite samples. Introduction of fluorite samples was carried out using the spill-injection method simultaneously with high pure calcium oxide introduction using the second conveyor belt. The use of an additional photodetector array with a spectral range of 528 – 536 nm provides the possibility of expanding the spectrum of CaF molecular lines with the intensity sufficient for determination of fluorine concentrations in fluorite samples. A calibration curve for fluorine determination in a concentration range of 0.12 – 47.63% was plotted using measurement results for 200 fluorite samples. Integration of the additional photodetector array provided increased detection limit for the mass fractions of fluorine up to the maximum possible concentrations in fluorite samples. The observed effect simplifies and speeds up the analysis in the absence of the necessity to dilute the sample, thus reducing the error of measurements. The results show that there is no need to introduce additional buffer mixtures (except CaO) and use reference lines to determine the fluorine concentration, which also simplifies the measurement procedure.