The realization of independent and controllable key core technologies is an important engine for central state-owned enterprises to give full play to the “chain length” function of the industrial chain, lead industrial technology breakthroughs, and seize the commanding heights of scientific and technological competition and future development. However, existing literature has not yet carried out in-depth research on the formation conditions and mechanisms of key core technology breakthroughs in central state-owned enterprises. Based on the resource-based view and the dynamic capability theory, this paper incorporates the TOE analysis framework and employs fsQCA to explore the interactive effects and driving paths of resources, capabilities, and environmental conditions in promoting key core technology breakthroughs in central state-owned enterprises. The findings are as follows: (1) Key core technology breakthroughs in central state-owned enterprises have the characteristics of “multiple concurrency” and “common destination”, and no single factor can independently constitute the necessary conditions to promote the key core technology breakthroughs. (2) There are five driving paths that promote key core technology breakthroughs in central state-owned enterprises, which can be summarized into four paradigms: internal-resource driven, external-environment empowered, resource-capability co-evolution, and multi-dimensional touchpoint linkage. (3) R&D investment, innovation output, and key human resources, as the unique resource and capability endowments of central state-owned enterprises, serve as the internal supporting forces for the key core technology breakthroughs. Meanwhile, enterprise collaborative innovation and innovation boundaries play the role of “booster” in the key core technology breakthroughs. This paper enriches and expands the theoretical research on key core technology breakthroughs in central state-owned enterprises, providing a theoretical basis for China to further break through the western technology blockade, overcome the “bottleneck” problem, and realize scientific and technological self-reliance.