Solving the healthy and coordinated development of rural population-land-industry (PLI) elements is a primary manifestation of overcoming extreme poverty. It holds significant importance for promoting comprehensive rural revitalization and achieving global sustainable development. Based on panel data from 80 county-level spatial units in the Qinling-Daba Mountains of China from 2010 to 2020, this article explores the spatial coupling and coordinated development relationship of rural PLI elements. It provides decision-making references for poverty-stricken mountainous areas’ rural revitalization and regional sustainable development. The research results show that the rural PLI elements in the Qinling-Daba Mountains are at a relatively low level. The population is mainly concentrated in the east and west, while arable land is primarily distributed in basins and valleys. The industrial distribution is typical in the southern foothills of Daba Mountain and Nanyang Basin. The static coupling degree has gone through a stage of adjustment and high-level coupling interweaving, while the dynamic coupling degree is mainly negative in terms of PLI development. The coupling coordination of rural PLI elements is mainly at a primary coordination level, with regional differences between high-value and low-value areas mainly related to terrain. Economic development and the natural environment have the most significant impact on the coordinated development of rural PLI coupling. Therefore, in the future, the Qinling-Daba Mountains should focus on coordinating the relationship between the natural environment and economic development, enhancing regional system innovation capabilities and research on land spatial governance strategies to promote high-quality development in the region. This study provides new insights into the coordinated development of rural PLI coupling in China’s concentrated contiguous poverty-stricken areas. It also offers decision-making references for achieving high-quality sustainable development in rural areas of other poverty-stricken regions worldwide.