As a vital avenue for seeking external heterogeneous resources and knowledge, executive interlocks empower specialized, refined, distinctive, and innovative (SRDI) enterprises to make breakthroughs in key core technologies. Using listed enterprises from the first five batches of SRDI “Little Giants”, this paper thoroughly investigates the impact of executive interlocks on breakthroughs in key core technologies and its contextual conditions, drawing on theoretical analysis and empirical examinations. The results show that: (1) Executive interlocks have a significant promoting effect on breakthroughs in key core technologies of SRDI enterprises. (2) Compared to local executive interlocks, cross-regional executive interlocks have a stronger promoting effect on breakthroughs in key core technologies. (3) Compared to within-industry executive interlocks, cross-industry executive interlocks have a stronger promoting effect on breakthroughs in key core technologies. In theory, this paper reveals the micro-mechanisms and boundary conditions for SRDI enterprises to achieve breakthroughs in key core technologies, thereby expanding the theoretical boundaries of research on SRDI enterprise innovation, as well as the relationship between geographical proximity and innovation, and deepening research on the innovation effects of the industrial relatedness of executive interlocks. In practice, it provides empirical evidence for SRDI enterprises to reconfigure innovation resources to drive breakthroughs in key core technologies.