Abstract Carbon dioxide, as a liquid (LCO 2 ) in subcritical state, was applied for extraction of carotenoids from ground paprika. The increasing polarity of LCO 2 with the decrease of its temperature enabled fractionation of pigments according to their increasing polarity. The main constituents of the fractions of +6 °C and −6 °C were triacylglycerols (TAGs) including a small concentration of β-carotene. At −16 °C, more polar pigments (capsorubin, capsanthin, zeaxanthin) and their fatty acid (FA) esters were extracted. The pre-concentration ratio of carotenoids in the fraction at -16 °C was 17.2 with respect to Fraction at +6 °C. In the FA composition (GC) of the fraction at −16 °C, (11.9%) prevailed lauric acid (C 12:0 ) and also myristic (C 14:0 , 8.2%) and palmitic (C 16:0 , 18.0%) acids. Linoleic (C 18:2 ) and linolenic (C 18:3 ) acids amounted to 19.4% and 3.1%, respectively. In contrast to the fraction at −16 °C, in the hexane/ethyl ether paprika extracts, unsaturated linoleic (C 18:2 , 59.4%) and linolenic (C 18:3 , 5.1%) acids prevailed.