Iron is a crucial resource for societal and economic progress. How can the China's iron industry, having grown in size and gained an export advantage, seek partners in the industry chain to develop better growth potential? We propose "relational upgrading" across multi-hierarchy. Using a Three-Stage Least Squares approach, we analyze the impact of three key network centralities of iron products on industrial upgrading, based on 1995–2020 HS-4 coded product export data. Results show: China's iron product network is multi-hierarchy. Relational upgrading transcends export advantage enhancement and reflects jumps to higher at multi-hierarchy. Policymakers can evaluate industry competitiveness by monitoring the iron product network's hierarchy of upgrades. Degree and betweenness centrality have a significant "inverted-U" effect on the iron industry's upgrading, while closeness has a hindering effect. Upgrading relationships across multi-hierarchy consolidates the network centrality status of iron products. Some policies for sustainable development as indicated by the results are given.