Fatty acid composition as an indicator of purity suggests that linolenic acid content could be used as a parameter for the detection of extra/virgin olive oil fraud with 5% of soybean oil. The adulteration could also be detected by the increase of the trans-fatty acid contents with 3% of soybean oil, 2% of corn oil, and 4% of sunflower oil. The use of the ΔECN42 proved to be effective in Chemlali extra-virgin olive oil adulteration even at low levels: 1% of sunflower oil, 3% of soybean oil, and 3% of corn oil. The sterol profile is almost decisive in clarifying the adulteration of olive oils with other cheaper ones: 1% of sunflower oil could be detected by the increase of Δ7-stigmastenol and 4% of corn oil by the increase of campesterol. Linear discriminant analysis could represent a powerful tool for faster and cheaper evaluation of extra-virgin olive oil adulteration.