Utilization of fly ash is of great importance in China in the context of resource and environmental crises. Different fly ash utilization processes are proposed, and some have been practically applied. However, none of these fly ash utilization pathways has been evaluated comprehensively by integrating both environmental and economic perspectives. In this study, three high-aluminum fly ash utilization methods in Mongolia were assessed and compared based on the concept of eco-efficiency. The environmental assessment was conducted in accordance with life-cycle assessment principles, and a monetization-weighting approach was applied to obtain social willingness-to-pay as a reflection of environmental impact. The environmental assessment results revealed that the reuse of fly ash had significant advantage for saving primary resource, while solid waste, depletion of water, and global warming were the three highest environmental impacts from the life cycle perspective. The economic performance assessment showed positive net profits for fly ash utilization, but high value-added products were not necessarily indicative of better economic performance due to the relatively high operation cost. Comparison of the eco-efficiency indicators (EEIs) implied that the process of scenario 1#, which produced mullite ceramic and active calcium silicate, was the most recommended out of the three scenarios on the present scale. This judgment was consistent with the evaluation of the resource utilization rate. The present study showed that the EEI could be used to compare different fly ash utilization processes in a comprehensive and objective manner, thus providing definitive and insightful suggestions for decision-making and technical improvement.