In this chapter, we focus on the difficulties children face when learning place value and how current psychological theories of relational learning may be leveraged by teachers. We discuss two major psychological mechanisms known to support relational learning--statistical learning and structure mapping--and review the evidence showing how these mechanisms are implicated in place value learning. We further identify a set of four specific instructional elements teachers could use to engage and support these learning mechanisms. We also review three major curricula for teaching place value, including "Developmentally Appropriate Mathematics," "Number Talks," and the "Montessori Method," in light of this conceptual framework. Our review highlights both strengths of these current curricula and ways they might be modified to more fully leverage relational learning mechanisms and increase student learning. [For the complete volume, "Constructing Number: Merging Perspectives from Psychology and Mathematics Education. Research in Mathematics Education," see ED616587.]