The implementation of the Beijing, Tianjin, and Hebei coordinated development strategy has seriously increased the influence of land use and urban traffic. Thus, understanding the coordination between urban land and transportation systems is important for the efficient and sustainable development of cities, especially in this rapidly urbanizing era. Urban–industrial land and highway networks are, respectively, primary types of urban land and transportation systems, and have significant impacts on social and economic development. However, limited studies have been conducted to examine the relationships between urban–industrial land and highway networks. Therefore, this paper aims to examine the coupling coordination relationship between urban–industrial land use efficiency, and the accessibility of the highway networks of cities. Specifically, in the context of the Beijing–Tianjin–Hebei (BTH) urban agglomeration, the coupling coordination between urban-industrial land use efficiency and accessibility of the highway traffic network was empirically analyzed. The results show that: (i) The differences in urban-industrial land use efficiency in the BTH region are significant. Capital cities in the BTH urban agglomeration have higher economic, social, and comprehensive efficiency, while in industrial cities, the use of urban–industrial land should prioritize ecological and environmental issues. (ii) Because of its good geographical location Beijing has the best accessibility, with an accessibility index of 1.416, while Qinhuangdao had the lowest accessibility index of 0.039. (iii) In most BTH cities, the urban-industrial comprehensive land use level has fallen behind the highway network development level. The results of this study can provide references for the coordinated development of the BTH urban agglomeration.