Traditional investigation procedures of soil and groundwater contamination are followed by soil gas sampling, soil sampling, groundwater sampling, establishment of monitoring wells, and groundwater monitoring. It often takes several weeks to obtain the analysis reports, and sometimes, it needs supplemental sampling and analysis to delineate the polluted area. Laser induced fluorescence (LIF) system is designed for the detection of free-phase petroleum pollutants, and it is suitable for on-site real-time site investigation when coupling with a direct push testing tool. Petroleum products always contain polycyclic aromatic hydrocarbon (PAH) compounds possessing fluorescence characteristics that make them detectable through LIF detection. In this study, LIF spectroscopy of 5 major fuel products was conducted to establish the databank of LIF fluorescence characteristic spectra, including gasoline, diesel, jet fuel, marine fuel and low-sulfur fuel. Multivariate statistical tools were also applied to distinguish LIF fluorescence characteristic spectra among the mixtures of selected fuel products. This study successfully demonstrated the feasibility of identifying fuel species based on LIF characteristic fluorescence spectra, also LIF seemed to be uncovered its powerful ability of tracing underground petroleum leakages.