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The notion of effectual networks is one of the central concepts in the effectuation research. However, there has been little conceptual and empirical work on how they emerge and what structures they have. This article incorporates the concept of complex adaptive systems from complexity theory to understand both their dynamic and structural elements. We examine the effectual networks and networking of 10 startups from Finland and offer a process-system model of effectual networks. We derive propositions that connect dynamic and structural entrepreneur-related factors of their emergence and outline directions for future research at the intersection of effectuation and complexity theory.