High energy-consuming industries are expected to play a significant role in energy conservation and emissions reduction. This study collects data on China's high energy-consuming listed companies from 2009 to 2022. Using the complex network theory, we construct a multilayer asset association network for high energy-consuming enterprises and examine how different layers and totality affect default risk. The results revealed that node-weighted degree centrality in the asset association networks of high energy-consuming enterprises, particularly in the guarantee association network, significantly increased default risk. Further mechanistic analysis reveals that the level of green technical cooperation innovation mitigates the impact of increased weighted degree centrality on the default risk of high energy-consuming enterprises. For high energy-consuming enterprises located in the eastern region, central region or non-heavily polluting industries, the influence of weighted degree centrality in the asset association network on default risk is more significant. This study enriches complex network research and provides guidance for managing default risk in high energy-consuming enterprises. Additionally, these studies align with global trends toward enhanced asset transparency, sustainability, and financial resilience, and contribute emerging markets to the transition toward more sustainable energy practices.