Monodispersed yttrium aluminum garnet (YAG) crystallites with welldeveloped and controllable crystal faces were obtained by the solvothermal method. The effects of temperature, time, and solvents on the phase formation, morphology, and particle size distribution were investigated. YAG can be obtained at relatively lower temperature in water, while higher temperature and longer time are necessary with increasing amount of ethanol in the solvent. The presence of {100} faces is favored at lower temperature while the terminating faces are {110} and {211} at higher temperature in water and water− ethanol mixture (volume ratio = 1:1). Moreover, solvent exhibits a significant influence on the reaction process, luminescence intensity, and decay time of YAG:Ce crystallites. This study presents a novel way to obtain YAG crystallites with well-developed terminating faces which will be promising in the solid-state lighting and will lay a foundation to study the grain boundaries formed in the process of YAG transparent ceramics sintering.