The reappearance of measles in the US and Europe, a disease considered eliminated in early 2000s, has been accompanied by a growing debate on the merits of vaccination on social media. In this study we examine the extent to which the vaccination debate on Twitter is conductive to potential outreach to the vaccination hesitant. We focus on Italy, one of the countries most affected by the latest measles outbreaks. We discover that the vaccination skeptics, as well as the advocates, reside in their own distinct “echo chambers”. The structure of these communities differs as well, with skeptics arranged in a tightly connected cluster, and advocates organizing themselves around few authoritative hubs. At the center of these echo chambers we find the ardent supporters, for which we build highly accurate network- and content-based classifiers (attaining 95% cross-validated accuracy). Insights of this study provide several avenues for potential future interventions, including network-guided targeting, accounting for the political context, and monitoring of alternative sources of information.