Fourier transform spectroscopic measurements of the absorption bands of the Herzberg I system [Formula: see text] of O2, have been made in the wavelength region 240–270 nm. Rotational line positions are determined with an accuracy of 0.005 cm−1, and rotational term values are presented for the vibrational levels, ν = 4–11. Molecular constants of these levels are also presented. Interactions with the [Formula: see text] state are observed at J = 13 of the ν = 4 level, at J = 16 of the ν = 7 level, and at J = 15 and 24 of the ν = 9 level of the [Formula: see text] state. Another interaction around J = 10 of the ν = 11 level might result from the weakly bound 3Πu state.