Photoluminescence studies have been carried out on liquid‐encapsulated Czochralski GaAs crystals. Two wafers (labeled P1 and P2) originating from the same ingot have been investigated. After close‐contact annealing, the presence of a &bartil;64‐meV deep acceptor was observed in P1‐type samples only. After gallium implantation at increasing doses and annealing, the presence of the &bartil;64‐meV level is also observed in P2‐type samples. Boron implantation at increasing doses also generated the 64‐meV level and, in addition, the &bartil;77‐meV acceptor level, often ascribed to GaAs. Using scaling arguments the 64‐meV level is tentatively ascribed to the first level of a double‐acceptor defect. Owing to the stoichiometric imbalance induced by implantation and annealing and the specific influence of boron implantation, the &bartil;64‐ and &bartil;77‐meV levels are tentatively ascribed to GaAsand BAsantisite defects, respectively.