We have grown GaAsBi quantum wells by molecular beam epitaxy. We have studied the properties of a 7% Bi GaAsBi quantum well and their variation with thermal annealing. High-resolution X-ray diffraction, secondary ion mass spectrometry, and transmission electron microscopy have been employed to get some insight into its structural properties. Stationary and time-resolved photoluminescence shows that the quantum well emission, peaking at 1.23 μm at room temperature, can be improved by a rapid annealing at 650°C, while the use of a higher annealing temperature leads to emission degradation and blue-shifting due to the activation of non-radiative centers and bismuth diffusion from the quantum well.