This article discusses the potential of mixed-method social network analysis (MMSNA) as a methodology for designing and conducting studies that address questions of interplay between human agency and social structures in educational settings. First, we discuss a rationale for using MMSNA referring to the theoretical calls for better understanding the role of agency in network structures. Next, we discuss examples of studies that illustrate how MMSNA has been applied to investigate (a) the role of agency in social network formation and (b) how social networks facilitate actors' agency in educational processes. Finally, we outline a guide for how to use MMSNA and consider its potential for future studies of interactions between agency and structures in educational settings.