Nonmonotonic composition dependence is often observed for numerous properties in the aqueous mixtures of small amphiphilic molecules. The molecular picture underlying this structure-activity relationship, however, remains largely elusive. We herein studied water reorientation dynamics in the aqueous mixture of dimethyl sulfoxide (DMSO), which has a significant nonmonotonic composition dependence, using molecular dynamic simulation and an extended molecular jump model. The analysis indicates that this nonideal behavior is driven by the collective frame diffusion component of water reorientation, which decelerates in the water-rich regime because of the strengthened hydrogen bonds and accelerates in the water-poor regime as the hydrogen bonding network is broken into smaller aggregates. The current work therefore connects the microheterogeneity in the solvation structure of DMSO-water with its nonmonotonic hydration dynamics and sheds new light on how microsegregation leads to the multiscale hydration nonideality in general.