Monocropping systems, which currently dominate China’s major grain production regions, contribute to resource scarcity and environmental pollution. Intercropping has the potential to improve resource use efficiency. However, prior studies of intercropping systems have generally focused on ecological, economic, and social consequences. Here, we make a comparative ecological sustainability analysis on energy capture and efficiency of maize monocropping and maize–soybean intercropping systems through emergy evaluation based on field experiments performed from 2012 to 2014. We find that maize monocropping shows higher sustainability than maize–soybean intercropping in the North China Plain at present. Quantitative results indicate that for maize monocropping, the emergy yield ratio (EYR) and emergy sustainability index (ESI) are 13.7% and 21.1% higher than that of intercropping systems, and the environmental loading ratio (ELR) is 7.3% lower than that of intercropping systems. To further test, we applied three levels of nitrogen fertilizer in intercropping systems (120 kg ha⁻¹, 180 kg ha⁻¹, 240 kg ha⁻¹), and find that a reduced rate of N fertilizer for intercropped system leads to higher sustainability (ESI 5.3% higher) but still lower sustainability than maize monocropping. Key drivers of the different sustainability outcomes are decreased energy output and a larger proportion of labor input associated with intercropping systems.