In recent years, the United States has intensified its technological blockade, posing severe challenges to the innovation and development of Chinese firms. However, amid the escalating China-US technology rivalry, many high-tech firms have managed to overcome foreign technological constraints and achieve breakthroughs in key core technologies. Using Chinese listed high-tech firms from 2016 to 2024 as the research sample, this study employs a staggered difference-in-differences model and draws on the Awareness-Motivation-Capability (AMC) perspective to examine the impact and underlying mechanisms of the Entity List on key core technological innovation among peer firms. The results show that the Entity List generates a significant positive spillover effect on peer firms’ key core technological innovation, and this effect remains robust after a series of robustness tests. Further, this study develops a theoretical framework of innovation spillovers induced by the Entity List, revealing that threat perception, dynamic competition, and cooperative empowerment jointly drive peer firms’ core technological breakthroughs through an AMC linkage path of “risk awareness-competitive motivation-industry collaboration”. Finally, through in-depth case analyses of GigaDevice and Juhua Group, this study further uncovers the complex mechanisms through which the Entity List exerts innovation spillover effects on peer firms. This study extends the research boundary of innovation spillovers from the Entity List and provides theoretical insights and empirical evidence for Chinese high-tech firms seeking to overcome technological blockades and enhance independent innovation capabilities.