In November 9, 2014, the Catalan government called Catalan people to participate in a straw poll about the independence of Catalonia from Spain. This article analyzes the use of Twitter between November 8 and 10, 2014. Drawing on a methodology developed by Guerrero-Solé, Corominas-Murtra, and Lopez-Gonzalez, this work examines the structure of the retweet overlap network (RON), formed by those users whose communities of retweeters have nonzero overlapping, to detect the community structure of the network. The results show a high polarization of the resulting network and prove that the RON is a reliable method to determinate network community structures and users’ political leaning in political discussions.