Abstract Detecting science–technology hierarchical linkages is beneficial for understanding deep interactions between science and technology (S&T). Previous studies have mainly focused on linear linkages between S&T but ignored their structural linkages. In this paper, we propose a network coupling approach to inspect hierarchical interactions of S&T by integrating their knowledge linkages and structural linkages. S&T knowledge networks are first enhanced with bidirectional encoder representation from transformers (BERT) knowledge alignment, and then their hierarchical structures are identified based on K‐core decomposition. Hierarchical coupling preferences and strengths of the S&T networks over time are further calculated based on similarities of coupling nodes' degree distribution and similarities of coupling edges' weight distribution. Extensive experimental results indicate that our approach is feasible and robust in identifying the coupling hierarchy with superior performance compared to other isomorphism and dissimilarity algorithms. Our research extends the mindset of S&T linkage measurement by identifying patterns and paths of the interaction of S&T hierarchical knowledge.