Pressure dependences of luminescence intensities of the I₂ (E 0_g⁺ → B 0_u⁺, D 0_g⁺ → X 0_g⁺ and β 0_g⁺ → A 1_u) transitions, temporal histories of the luminescence and luminescence excitation spectra at different time delays from the beginning of the probe laser pulse under OODR photolysis of the I₂ + SF₆ mixture have been measured. A comparison of experimental dependences with those obtained after detailed analysis of kinetics of spontaneous and collision-induced processes in a free iodine molecule has been made. We have established that there is additional optical channel of population of the I₂(β) state, namely, direct optical pumping of the SF₆I₂(IP) complexes, accompanied by their predissociation to the SF₆ + I₂(β) products.