Abstract Sesamolyl and related phenoxyl radicals were studied by conventional and time-resolved electron paramagnetic resonance (EPR) spectroscopic techniques. Continuous UV irradiation of sesamol in benzene produces two types of radicals. Based on the hyperfine coupling values obtained we determined that one is the neutral sesamolyl radical and the others are the dimer radicals. Comparison was made with related compounds, especially 3,4-dime-thoxyphenol. We found that the 3,4-dimethoxyphenoxyl radical had a shorter lifetime than the neutral sesamolyl radical. The EPR results obtained suggest that a near perpendicular orientation of the oxygen p-orbitals with respect to the benzene ring of sesamol makes the radical more stable. This stability may be important for the antioxidant properties.