The stability of highly consumed vegetable refined oils after discontinuous frying of potatoes was compared. Both those vegetable oils containing additives and those that did not were considered. Vegetable oil samples were evaluated using refractive index, anisidine and peroxide values, UV absorbance and dielectric constant-based determination of the content of total polar compounds. Chemical changes caused over the frying time were monitored and multivariate modelling of the data was carried out. A new gas chromatographic-mass spectroscopy method was intended to record a fingerprint of both polar and non-polar compound fractions. Multivariate models of chromatographic fingerprints were also developed, and the results obtained from both approaches were verified to be statistically similar. In addition, multivariate modelling also allows to differentiate among vegetable oils according to oxidation performance. Indeed, it was initially observed that olive oils presented the highest natural thermo-oxidative stability compared to other seed oils, although it should be noted that these differences were not significant when regarding olive pomace oils and seed oils containing synthetic additives.