We present a detailed study on the optical properties of GaAsBi/GaAs multiple quantum well structure, optimized for the active area for vertical-external-cavity surface-emitting lasers. The quantum structure was grown by molecular beam epitaxy with every other barrier made thinner to have a homogeneous structure with high photoluminescence (PL) intensity. PL measurements were carried out in a wide temperature range from 4 to 300 K. The PL band of 1.085 eV was attributed to the optical transition in QWs with 8.0%Bi. The S-shaped temperature dependence of PL peak positions showed high localization effect of 30 meV. The internal quantum efficiency (IQE) was evaluated for the bismide structures with a modified ABB* method, which includes contribution from trap-assisted Auger recombination. The calculations showed low IQE of <0.025% for GaAs0.92Bi0.08/GaAs 12 QWs structure, which was explained by the low growth temperature, resulting in a high density of point defects in the material.