Political vigilantism has come out as an offshoot of the violence that characterises multi-party elections in Ghana. Several studies on political vigilantism give primacy to the role of structural factors in explaining the phenomenon in Ghana. However, such a notion deprives political vigilantes of any sense of agency and further evades how the understanding of the interaction between agency and structure can offer deeper insights into the phenomenon of political vigilantism. The paper argues that political vigilantes should be characterised as agents who can make decisions about the actions that they undertake and not solely determined by the constraints of structure. The actions of political vigilantes are mediated through social structures that shape the options available to them. Using purposive and snowball sampling techniques, 41 key informants were selected for the study in Accra, Kumasi and Tamale. The study employed both primary and secondary data sources. Whereas secondary data was sourced from desk reviews, primary data was collected through interviews and focus group discussions. The narratives were thematically analysed. The study findings show that members of political vigilante groups are conscious agents and for that matter decide and act either autonomously or relationally despite existing pressures from social structures. In addition, the paper shows that the exercise of agency among the vigilantes is inseparable from structure as the structure is reproduced and changed through the actions of the political vigilantes who in turn are shaped through the structures that they occupy. Therefore, policy responses to political violence should consider the two sides of the equation by working simultaneously on the behaviour of political actors and resolving the circumstances that facilitate political violence