On the basis of the source of illegal cooking oil (heated vegetable oil and animal oil) and the important referents reflecting their sources, namely, undecanoic acid and 13-methyl-tetradecanoic acid connected to the glyceride, their corresponding ramifications in edible oil were detected with internal standard method. The sensitivity and selectivity of this method were improved by the on-line cleanup and preconcentration. The detection limits of the method were 0.070 mg/kg for undecanoic acid and 0.006 mg/kg for 13-methyl-tetradecanoic acid. Additionally, most of the normal vegetable oils have lower levels of both fatty acids than illegal cooking oils. It was suggested to evaluate the quality of edible oils to some extent on the basis of the contents of undecanoic acid and 13-methyl-tetradecanoic acid.