There are four major problems related to fuel consumption, “large consumption”, “low quality”, “lack of front-end clean” and “lack of end emission control”, which needs to address urgently for our country. More than 60 percent of the air pollution is due to the burning of coal and oil in our country, so the haze problem depends on how much we can deal with energy issues. We should achieve the identification and measurement of gasoline, diesel, kerosene and other refined oil products rapidly and accurately, which is important for the implementation of air pollution monitoring and controlling. in order to characterize the type information of the refined oil accurately and to improve the efficiency of the network model identification, it is effective to use principal component analysis method which could achieve the data dimension reductionwhile reducing the complexity of the problem. With principal component analysis of the most commonly used three-dimensional fluorescence spectra based on excitation-emission matrix (Excitation-Emission Matrix, EEM) data, we could obtain finer, deeper characteristic parameters. During the process of classification, it could avoid the “over-fitting” phenomenon because of the application of the cross-validation method, A neural network capable of both qualitative and quantitative analysis is designed. The neural network pattern recognition result becomes feedback to the input of the concentration network, together with the relative slope, the comprehensive background parameters, and the relative fluorescence intensity, we could achieve the measurement of the concentration of the corresponding types, then use the extension neural network pattern recognition technology to achieve identification and measurement of kerosene, diesel, gasoline and other refined oil products. The results of the study show that the average recognition rate reaches 0.99, the average recovery rate of concentration reaches 0.95, the average time of pattern recognition is 2.5 seconds and this time is 48.5% of the time used by PARAFAC model analysis method. The method significantly improves the operation speed with ideal application effect . It should be pointed out that, in order to ensure the accuracy and precision of the analysis, we should make corresponding calibration samples for specific analytes in terms of the analysis of complex mixtures such as refined oil, pesticides, tea, etc.