FAαPbBr2+α composite perovskites consisting of 0D FA4PbBr6 and 3D FAPbBr3 have been synthesized by a solid state reaction. Due to the endotaxy passivation of FAPbBr3 by FA4PbBr6, FAPbBr3 crystals were stably deformed without agglomeration from the cubic to the orthorhombic structure by compression, which led to a significant PL enhancement.