New all-inorganic perovskites like Cs4PbBr6 provide rich luminescent tools and particularly novel physical insights, including their zero-dimensional structure and controversial emitting mechanism. The ensuing debate over the origin of the luminescence of Cs4PbBr6 inspired us to tackle the issue through fabricating high-quality Cs4PbBr6 single crystals and employing ultrafast dynamics study. Upon photoexcitation, Cs4PbBr6 underwent dynamics steps distinct from that of CsPbBr3, including exciton migration to the defect level on a time scale of several hundred femtoseconds, exciton relaxation within the defect states on the picosecond time scale, and exciton recombination from the subnanosecond to nanosecond time scale. The observation disclosed that crystal defects of Cs4PbBr6 induced green emission while CsPbBr3 mainly relied on quantum confinement to emit at room temperature. The study provides an in-depth understanding of the photoinduced multistep dynamics steps of Cs4PbBr6 associated with display and photovoltaic applications, establishing Cs4PbBr6 as a new candidate for uses associated with the perovskite family of materials.