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The topic of defection has been investigated along three major theoretical lines by sociologists; grievances, rational choice theory, and identity and intra-group pressure. No sociologist has explored defection from a social movement’s perspective, which is what this paper seeks to do. The overarching research question assesses the framing processes, political opportunities, and mobilising structures of National Armed Forces defectors during the Libyan revolution of 2011 to uncover how and why they defected. Semi-structured interviews were conducted with National Armed Forces defectors, revolutionaries, and Gaddafi supporters in order to assess the micro-mobilisation dynamics of defection. The paper concludes that defection is a social process, and not an action, as some rational choice theorists suppose and that the involvement of NATO forces served to create significant political distance between a population that was somewhat united in its desire for improved social and economic conditions. The paper also calls for further research on micro-mobilisation to be undertaken using a combination of grievances and social pressure explanations, in combination with political opportunities, mobilisation structures, and framing processes, as the first two elements primarily assess the individual defector and the latter three focus more on the contextual elements of the defection.