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Low‐temperature (∼4 K) photoluminescence has been studied on as‐grown and thermally annealed Si‐doped GaAs grown by molecular beam epitaxy. The peak intensities of the defect‐related emissions, due to the defect‐induced bound exciton (d, X) and the defect complex (d) are decreased by thermal annealing. On the other hand, Hall measurements show that free carrier concentrations are decreased only slightly by thermal annealing.