Eliminating poverty and upgrading the industrial structure are major challenges faced by contiguous poverty-stricken areas in the three-year campaign against poverty. Since the national strategy of targeted poverty alleviation was put forward, the tourism industry has become one of the crucial avenues through which residents increase their income, optimize the industrial structure, promote economic development, and escape the poverty trap. It is therefore urgent to study the coupling coordination relationship between industrial structure transformation and upgrade and tourism poverty alleviation efficiency. Taking the 42 national poverty-stricken counties in the Wuling Mountain Area as examples, the SBM model and improved entropy method are applied to measure the tourism poverty alleviation efficiency and industrial structure transformation and upgrading index, respectively. The coupling coordination model is then employed to describe the spatio-temporal evolution characteristics of the coupling coordination relationship between industrial structure transformation and upgrade and tourism poverty alleviation efficiency in the Wuling Mountain Area. The results are as follows. (1) The industrial structure transformation and upgrading index of the study area as a whole and each sub-area shows irregular changes, and the future development trend is not obvious. Tourism poverty alleviation efficiency declined slightly at the end of the sample period in Hunan and Guizhou subareas, while Hubei and Chongqing subareas showed a significant upward trend. (2) The uncoupled and uncoordinated county units of industrial structure transformation and upgrade and tourism poverty alleviation efficiency are concentrated in the central part of Wuling Mountain Area, and the number of units decreased annually. The number of counties that achieved coupling and coordination increased significantly and presented an agglomeration trend to the edge zone. (3) The transition from uncoupling disorder (type 1) to coupling coordination (type 2) is the core transformation path, which leads to the fact that the number of type 2 regions increased significantly, and gradually formed a band distribution at the edges of the study area. Finally, based on the above research results, it is suggested that the poverty-stricken areas should actively strengthen the integrated development of tourism industry and other industries, and give full play to the two-way radiation effect of industrial structure transformation and upgrade and tourism poverty alleviation efficiency. This would reconstruct and optimize the coupling path and spatial distribution pattern of the two, which enables the coordinated development of industrial structure changes and poverty alleviation through tourism. In turn, this realizes the optimization and adjustment of the industrial structure in poor areas and allows for smooth poverty alleviation.