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Institutions seek to shape the behaviors of their constituents. Because individuals are embedded in complex webs of social relations, by shaping personal behaviors, institutions may unwittingly reshape network structure. In this paper, I introduce the concept of relational externalities — the unintended relational consequences of a policy or intervention. I elaborate two different forms that relational externalities commonly take, the mechanisms that bring them about, and the role they play in creating or amplifying inequalities. I then empirically illustrate this concept through the case of the punishment of smoking behavior in a sample of U.S. high schools. I show that harsh punishment of smoking behavior is associated with the social isolation of smokers and increased homophily on smoking status in friendship networks. A subsequent exploration of the mechanisms behind these effects reveals that they are likely driven by non-smokers eschewing friendships with smokers. Finally, I show that relational externalities of anti-smoking policies are most acute for students with the least behavioral elasticity with regards to smoking. Students who are least able to change their behaviors change their friends, putting them at a dual disadvantage.