This article aims to explore the relationships between classroom management and young children's peer relationships. The participants are six-year-old, twin brothers born to a Vietnamese immigrant woman in Taiwan. The data include observation notes, parent and teacher interviews, and documents of children's work and school records. The results reveal that, given their mother's limited language ability, the twin's ability to appropriately use different languages is well accepted by peers. In addition, during free play time, whether the teachers can allow children to flexibly use time and space is associated with children's peer relationships. Finally, it is more likely that positive peer relationships can be nourished, if teachers can positively state the expectations to children's behaviors, and give constructive feedbacks to inappropriate behaviors in private. Discussions of classroom management and the educational needs for immigrant women's children are also included.