The substitution of extra virgin olive oil with other edible oils is the primary method for fraud in the olive-oil industry. Developing inexpensive analytical methods for confirming the quality and authenticity of olive oils is a major strategy towards combatting food fraud. Current methods used to detect such adulterations require complicated time- and resource-intensive preparation steps. In this work, a comparative study incorporating Raman and infrared spectroscopies, photoluminescence, and thermal-conductivity measurements of different sets of adulterated olive oils is presented. The potential of each characterization technique to detect traces of adulteration in extra virgin olive oils is evaluated. Concentrations of adulterant on the order of 5% can be detected in the Raman, infrared, and photoluminescence spectra. Small changes in thermal conductivity were also found for varying amounts of adulterants. While each of these techniques may individually be unable to identify impurity adulterants, the combination of these techniques together provides a holistic approach to validate the purity and authenticity of olive oils.