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Abstract We investigate structural features and processes associated with the onset of systemic conflict using an approach which integrates complex systems theory with network modeling and analysis. We present a signed network model of cooperation and conflict dynamics in the context of international relations between states. The model evolves ties between nodes under the influence of a structural balance force and a dyad-specific force. Model simulations exhibit a sharp bifurcation from peace to systemic war as structural balance pressures increase, a bistable regime in which both peace and war stable equilibria exist, and a hysteretic reverse bifurcation from war to peace. We show how the analytical expression we derive for the peace-to-war bifurcation condition implies that polarized network structure increases susceptibility to systemic war. We develop a framework for identifying patterns of relationship perturbations that are most destabilizing and apply it to the network of European great powers before World War I. We also show that the model exhibits critical slowing down, in which perturbations to the peace equilibrium take longer to decay as the system draws closer to the bifurcation. We discuss how our results relate to international relations theories on the causes and catalysts of systemic war.