Due to the health benefits of extra virgin olive oil (EVOO) and its increasing consumption patterns, adulteration of these oils using lower grade olive oils like virgin olive oil (VOO) and then later sold as EVOO to unsuspecting consumers has become a concern in the industry. There is a need for quick, reliable and inexpensive detection techniques to unmask such vice in order to realize its benefits. In this study, adulteration of EVOO is made using VOO at different proportions; their Excitation Emission Matrices (EEM) were examined using Front-face fluorescence spectroscopy and their corresponding fluorescence images captured using 365 nm ultra-violet (UV) LED for analysis. Specific regions for both the EEM and imaging were explored using Support Vector Machine (SVM) classification analysis and their sensitivities evaluated using Partial Least Squares Regression (PLSR) analysis. It was found that EEM excitation 230-500 and emission 260-620 nm could easily discriminate between different samples as EVOO mixed (at different ratios) and VOO. The significant fluorescence peaks for the discrimination forms a combination of Tocopherols, Tocotrienols, Phenolic compounds, Oxidation products and Vitamin E. The results show that Front-face fluorescence spectroscopy and UV-induced fluorescence imaging can potentially discriminate between pure EVOO and adulterated olive oils.