The intrinsic photoluminescence Stokes shift, i.e., the energy difference between optical band gap and emission peak, of 350 μm thick semi-insulating GaAs wafers is found to be 4 meV at room temperature. The result is based on the determination of the optical bulk band gap from the transmission trend via modified Urbach rule whose result is confirmed with the transmission derivative method. The findings reveal the detailed balance of the optically evoked transitions and disclose the intrinsic link between Stokes shift and the Urbach tail slope parameter
