The construct professional noticing of children’s mathematical thinking is introduced as a way to begin to unpack the in-the-moment decision making that is foundational to the complex view of teaching endorsed in national reform documents. We define this expertise as a set of interrelated skills including (a) attending to children’s strategies, (b) interpreting children’s understandings, and (c) deciding how to respond on the basis of children’s understandings. This construct was assessed in a cross-sectional study of 131 prospective and practicing teachers, differing in the amount of experience they had with children’s mathematical thinking. The findings help to characterize what this expertise entails; provide snapshots of those with varied levels of expertise; and document that, given time, this expertise can be learned.