A considerable difference of iodine emission spectra after optical-optical double resonance excitation of the E0(g)(+), v(E) = 19, J(E) approximate to 55 and J(E) approximate to 85 rovibronic levels is observed. The latter include strong transitions from the gamma 1(u) ion-pair state to valence ones. This feature is interpreted as a result of hyperfine coupling of near-resonant E0(g)(+), v(E) = 19, J(E) = 81 and gamma 1(u), v(gamma) = 18, J(gamma) = 80 states. The hyperfine matrix element and dipole moment functions of transitions from the. state are estimated. The hyperfine g/u mixing of the iodine ion-pair states is observed for the first time.