In this paper, we question the implicit assumption that more entrepreneurship drives more innovation and growth, asserting that specific typologies of entrepreneurship are responsible for these phenomena. A growing number of studies has analyzed this relationship while focusing on the overall level of entrepreneurship. This paper exploits recent advancements in measuring the sophistication and connectedness of economic systems, brought by the notions of economic complexity and relatedness, to study the nexus of industrial structure and high-potential forms of entrepreneurship. The present study uses a panel dataset for Italy for the period 2015–2019. The results show a differentiated pattern among the high-potential startups considered, with relatedness and complexity having a positive effect for innovative startups, a negative one for high-growth startups, and no effect for pioneers. These results inform potential entrepreneurs of the importance of analyzing how external conditions can have distinctive effects on the process of opportunity identification among different typologies of high-potential startups.