The aim of the present study was to determine the spectrophotometric and thermal aging properties of various edible oils (olive, peanut, rapeseed, soybean and sunflower oils) which are commonly available in the Czech market. The samples were measured by UV/VIS absorption spectrometry and fluorescence spectroscopy. Detected substances of UV/VIS spectra were compared to expected oil composition; the highest absorbance values were detected in a wavelength range 300-550 nm which can be related to the presence of unsaturated fatty acids. The mixtures of oils were characterized by fluorescence spectroscopy; the individual oils were successfully distinguished according to their excitation-emission profiles. This method was also used to detect the samples of adulterated oils, i.e., the adulteration of high-quality oils with soybean oil. From a physicochemical point of view, the influence of temperature on the compounds of extra virgin olive oil was examined by thermal stress simulation. This thermal aging analysis demonstrated that the amount of oxidation products in olive oil increased during the heating whereas the chlorophyll content decreased. The results showed the ability of the techniques used, UV/VIS absorption spectrometry and fluorescence spectroscopy, to characterize the quality and composition of oils, and to distinguish individual oils in blends. UV/VIS spectrometry was also successfully employed for the evaluation of olive oil qualitative parameters according to the standard quality parameters by the "International Olive Council" (EEC 702/2007).