Using a sample of 14 prefecture-level cities in Liaoning Province, this study first explored the spatial hierarchy and structural characteristics of energy efficiency from the following three viewpoints: energy technical efficiency based on data envelopment analysis, energy consumption per unit of GDP, and energy utilization efficiency combining the previous two indexes. After measuring and analyzing the advancement, rationality, and concentration of the industrial structure in each city, we made some generalizations about the coupling features of the energy efficiency and industrial structure in Liaoning, using the coupling degree rating model. Some of our conclusions are as follows:(1) The 14 cities differ significantly in their energy efficiency, with Shenyang, Dalian, Anshan, and Jinzhou enjoying the highest energy efficiency. Northwestern Liaoning and other heavy-industrial cities such as Fushun and Benxi belong to low-efficiency and high-consumption areas.(2) In areas with higher efficiency, the spatial patterns of the energy technical efficiency, energy consumption per unit of GDP, and energy utilization efficiency are, respectively, " ? "-, "Ⅱ"- and "H"- shaped. Geographically, the energy utilization efficiency shows different trends from east to west and from north to south. Factors such as the binuclear structure of economic development have a major effect on this spatial pattern of energy efficiency.(3) Southeastern Liaoning enjoys a highly advanced industrial structure. Areas with a highly rational industrial structure form an "H" shape, with Shenyang and Dalian at the two poles. The urban agglomerations in middle and southern Liaoning have a highly concentrated industrial structure.(4) Overall, the coupling between energy efficiency and industrial structure is low in Liaoning, except for Shenyang and Dalian at both ends, where the coupling between an advanced industrial structure and energy efficiency is higher than in other cities.