The discrimination of virgin olive oils from other edible oils together with the detection and quantification of their adulteration is presented. FT-Raman spectra of 120 samples of fats and oils from 21 sources were analysed for these objectives. The usefulness of this technique is clearly demonstrated. An arborescent structure including 7 mathematical equations were designed to discriminate simultaneously saturated fats, corn, sunflower, soybean, canola, peanut, high oleic sunflower and virgin olive oils. The possibilities offered by spectral data in the detection of virgin olive oil was also investigated. Results show that genuine samples can be easily discriminated from adulterated samples including those spiked at 1%.