Abstract: The quantitative elemental content analysis is difficult due to the uniform effect, particle effect and the element matrix effect, etc, when using energy dispersive X-ray fluorescence (EDXRF) technique. In this paper, a hybrid approach of genetic algorithm (GA) and back propagation (BP) neural network was proposed without considering the complex relationship between the concentration and intensity. The aim of GA optimized BP was to get better network initial weights and thresholds. The basic idea was that the reciprocal of the mean square error of the initialization BP neural network was set as the fitness value of the individual in GA, and the initial weights and thresholds were replaced by individuals, and then the optimal individual was sought by selection, crossover and mutation operations, finally a new BP neural network model was created with the optimal initial weights and thresholds. The calculation results of quantitative analysis of titanium and iron contents for five types of ore bodies in Panzhihua Mine show that the results of classification prediction are far better than that of overall forecasting, and relative errors of 76.7% samples are less than 2% compared with chemical analysis values, which demonstrates the effectiveness of the proposed method.