( )Mayenite Ca12Al14O33, as an oxide-ion conductor, has the potential of being applied in many fields, such as solid-oxide fuel cells. However, its relatively low oxide-ion conductivity hinders its wide practical applications and thus needs to be further optimized. Herein, a new recently developed glass crystallization route was used to prepare a series of Ga-doped Ca12Al14-xGaxO33 (0 <= x <= 14) materials, which is not accessible by the traditional solid-state reaction method. Phase evolution with the content of gallium, the corresponding structures, and their electrical properties were studied in detail. The X-ray diffraction data revealed that a pure mayenite phase can be obtained for 0 <= x <= 7, whereas when x > 7, the samples crystallize into a melilite-like orthorhombic Ca5Ga6O14-based phase. The electrical conduction studies evidence no apparent enhancement in the total conductivity for compositions 0 <= x <= 7 with the mayenite phase, and therefore, the rigidity of the framework cations and the width of the windows between cages are not key factors for oxide-ion conductivity in mayenite Ca12Al14O33-based materials, and changing the free oxygen content through aliovalent cation substitution may be the right direction. For compositions with a pure melilite-like orthorhombic phase, the conductivities also mirrored each other and are all slightly higher than those of the mayenite phases. These melilite-like Ca5Ga6O14-based materials show mixed Ca-ion, oxide-ion, and electron conduction. Furthermore, the conduction mechanisms of Ca ions and oxide ions in this composition were studied by a bond-valence-based method. The results suggested that Ca-ion conduction is mainly due to the severely underbonded Ca3 ions and that the oxide ions are most likely transported via oxygen vacancies.