Abstract: The innovative breakthrough of key core technologies is not only an important means to break free from foreign technological blockades and ensure the security of China's industrial and supply chains, but also an inevitable choice to achieve technological self-reliance and high-quality development. However, this innovation process involves high technological uncertainty and high market uncertainty, which seriously weakens the innovation motivation of enterprises and puts higher demands on their capabilities. External policy opportunities, market opportunities, and technological opportunities provide a favorable environment for breakthroughs in key core technological innovation. How can the opportunity windows trigger key core technological innovation breakthroughs for enterprises? This issue is crucial. Previous studies have confirmed the impact of external opportunity windows on corporate technological innovation from the perspectives of learning and resources. However, there is a lack of effective explanation for the triggering mechanism and boundary conditions of the opportunity windows for key core technology innovation breakthroughs. The MOA theory builds a framework for analyzing the antecedents of organizational behavior that covers opportunities, motivations, and capabilities, providing an effective perspective on how opportunity windows affect key core technological innovation breakthroughs. This study constructs a moderated mediation model based on MOA theory and conducts empirical analysis using sample data from 315 companies in strategic emerging industries. The research results show that: (1) the technological opportunity window, market opportunity window, and policy opportunity window are external triggering conditions for breakthroughs in key core technological innovation. (2) Technical expectations and market expectations are important bridges connecting opportunity windows and breakthroughs in key core technology innovation, as well as internal driving forces for breakthroughs in key core technology innovation. (3) Technical capability is an important support for enterprises to bridge the gap between innovation expectations and actions. Enterprises with higher technical capabilities, stimulated by the opportunity windows, generate stronger technical and market expectations that drive breakthroughs in key core technology innovation. This study contributes to the literature in two ways. Firstly, the intermediary mechanism and boundary conditions that trigger breakthroughs in key core technology innovation through the opportunity windows were explored. Existing research are difficult to effectively explain the relationship between opportunity windows and key core technological innovation breakthroughs. On the basis of closely grasping the two uncertain characteristics of key core technology innovation breakthroughs, this study reveals the mechanism between opportunity windows triggering key core technology innovation breakthroughs, identifies the bridge role of innovation expectations between opportunity windows and key core technology innovation breakthroughs, and the supporting role of technological capabilities in transforming innovation expectations into key core technology innovation breakthroughs. This conclusion deepens the exploration of the roles of expectations and capabilities in the innovation process and enriches the research on the breakthrough mechanism of key core technology innovation. Secondly, it enriches the application research of MOA theory in the field of technological innovation. Current research mainly applies MOA theory to fields such as marketing management, organizational management, and knowledge management, focusing on revealing the impact of opportunities, motivations, and abilities on organizational behavior. This article expands the MOA theory to the field of innovation management and explores the relationship between opportunity windows and key core technology innovation breakthroughs, as well as the bridging role of motivation and the supporting role of capabilities. It provides new evidence and insights for the roles and roles of the three elements in MOA, and also expands the application scope of MOA theory in the field of technological innovation.