Abstract: In the context of “carbon neutrality”, the interdependence between the utilization of metal resources and the decarbonization of the electricity sector is increasingly pivotal. This paper constructs single-layer and multilayer complex network models using input-output tables and applies inter- and intra-layer communicability metrics to systematically capture the metal-electricity sector coupling nexus from the sectors perspective. The econometric regression model further reveals the implications of the nexus for carbon emissions in the electricity sector. The research results show that the changes of metal-electricity sector coupling nexus exhibit asymmetry from 2007 to 2020, with the electricity sector’s dependence on metal sector increasing substantially, while the metal sector’s dependence on electricity has declined in recent years. The metal-electricity sector coupling nexus is supported by other industries. In addition to the material support provided by the traditional electrical machinery and equipment industry, the electricity sector’s reliance on the metal sector also depends on capital, technology, and information services in recent years to meet the multifaceted demands of a low-carbon transition. The metal-electricity sector coupling nexus serves as a crucial mechanism for carbon emissions reduction, with both the electricity sector’s dependence on metal sector and the metal sector’s dependence on electricity sector showing significant negative impacts on carbon emissions. In regions with limited clean power capacity, high electricity production, heavy reliance on traditional energy, and lower economic development levels, enhanced support from the metal sector significantly reduces carbon emissions within the electricity sector. The interaction between the strategic metal sector and the wind-photovoltaic industry drives future changes in the metal-electricity sector coupling nexus. The coordinated expansion of the strategic metals → wind-photovoltaic industry chain is a vital pathway for the sustained reduction of carbon emissions in the electricity sector. Based on the above analysis, the following suggestions are proposed: to strengthen the detailed monitoring of economic interactions between the metal and electricity sectors to provide policymakers with informed decision-making support; to bridge collaboration gaps within the strategic metals → wind-photovoltaic industry chain and to enhance the integration of external service sectors; to identify key regions for supporting the strategic metals → wind-photovoltaic industry chain and to establish cross-provincial cooperation platforms to promote regional collaboration and resource sharing are essential steps forward.