The Rfvalues of ten antioxidants, namely several UOP, Permanax, Antozite, etc., have been calculated on the basis of their structures. The Rfcalcvalues have been compared with the experimental Rfvalues, obtained on reversed phase TLC plates. The variance of the calculated data around the experimental Rfvalues is 4.10−4. The approach allows a positive identification without reference substances or with a limited number of standards, which is the structure that gives Rfcalcvalues close to the Rfof the sample spots. Some considerations on the probable retention mechanism are also given.