Caffeic acid and (+)-catechin, which are abundantly contained in coffee and tea, are typical polyphenols. In order to know the relative magnitudes of antioxidant activity, effects by caffeic acid, (+)-catechin and their derivatives on the formation of 4-POBN/carbon-centered linoleic acid-derived radical adducts were examined in the control reaction mixture of linoleic acid with FeCl₃ at 30°C for 168 h. In the presence of 1.0 mM of the polyphenols, peak to peak heights of the third ESR signal resulted in 7.7 ± 2.4% ( n = 3) (caffeic acid), 145 ± 13% ( n = 3) (quinic acid), 4.4 ± 0.0% ( n = 3) (chlorogenic acid), 104 ± 4.4% ( n = 3) (ferulic acid), 4.3 ± 0.0% ( n = 3) (noradrenaline), 12.5 ± 10.9% ( n = 3) (gallic acid), 38.1 ± 7.1% ( n = 3) [(+)-catechin], 47.9 ± 11.7% ( n = 3) [(–)-epicatechin], 56.5 ± 1.6% ( n = 3) (epigallocatechin), 13.5 ± 1.7% ( n = 3) (catechol) and 83.7 ± 7.8% ( n = 3) (resorcinol) of the control reaction mixture. All the compounds with catechol moiety exerted potent inhibitory effects on the radical formation except for (+)-catechin, (–)-epicatechin and epigallocatechin. (+)-Catechin, (–)-epicatechin and epigallocatechin may not exert the inhibitory effect as much possibly because they are less stable compared with caffeic acid. The resorcinol moiety in these molecules may also weaken their antioxidant activity.