The reaction of GaCl₃ with 1 equiv of NHC ligand (NHC = N-heterocyclic carbene) at room temperature in pentane yielding the corresponding 1:1 adduct [GaCl₃(NHC)] is reported. Using IPr (N,N’-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), IMes (N,N’-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), and IPrMe (1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene), three NHC-containing GaIII adducts have been synthesized in good yields and fully characterized by ¹H and ¹³C NMR, HRMS, elemental analysis, and X-ray diffraction studies for the first time. The solid-state structure of [GaCl₃(IMes)] presented, as a special feature, two different positions of the main molecule with an occupation ratio of 50%. These positions of the molecule are shifted with respect to each other along the c-axis by 0.96 Å.