The objective of the research conducted was to select optimal parameters for a new method used to assess the quality of oils based on the determination of volatile compounds – oxidation products of those oils. Prior to the analysis, the samples of refined edible oils were oxidized during an accelerated oxidation process using UV irradiation (12 W, 254 nm). A technique used to prepare samples for analysis was the headspace solid-phase microextraction (HS-SPME). Optimal parameters of this technique were selected (DVB/CAR/PDMS fibre of 2 cm and of 50/30 µm; 8 ml volume of the sample; time and temperature of extraction: 15 min/30 °C, respectively). Additionally, some validation parameters were determined. The precision and sensitivity of this method, expressed as CV variation coefficient (< 10 %) and as LOD limit of detection (within the range from 162 to 346 µg/kg) appeared to be satisfactory for the determinations of this type. The composition of the samples analyzed was determined on the basis of standard compounds retention times using capillary gas chromatography with flame-ionization detector (column: SPB-20, Supelco, 30 m x 0,25 mm x 1 µm).