New urbanization often leads to land-use and land-cover change (LUCC), which inevitably affects ecosystem services (ESs). Although it is traditionally believed that urbanization reduces ecosystem services, some studies have shown that reasonable urban development facilitates ecosystem conservation. Previous studies have focused on the impacts of urbanization on either LUCC or ESs, with fewer dynamic assessments of the coordination of the three. Taking China’s contiguous poor areas (CPAs) as an example, this study applied coupling coordination, path analysis, and a multiscale geographically weighted regression (MGWR) model to identify the dynamic relationship among urbanization, land use, and the environment and then predicted their coupling coordination under shared socioeconomic pathways (SSP-RCP) in 2035 using the Patch Generation Land Use Simulation (PLUS) and a random forest model. The results of the study show that (1) urbanization, land-use change, and environmental loads in China’s CPAs showed an inconsistent upward trend. There was a slight overall decrease in ESs before 2013, which was consistent with the early stage of the Environmental Kuznets Curve (EKC); after that time, they showed different characteristics. (2) From 2000 to 2018, the coupling coordination degree of CPAs decreased slightly due to urbanization, geographic factors, and grassland and unused land. LUCC was essential to maintaining the system balance. The SN (southern contiguous poverty area) was at a basic level of coordination, while the other regions showed a moderate imbalance. (3) According to scenario projections, the degree of coupling coordination in all regions will increase by 2035. Environmental prioritization and sustainable routes are the best options for CPAs’ development. The SN is more stable, while the WN (western contiguous poverty area) has the lowest coupling coordination. (4) Environmentally friendly urbanization should be carried out with land management tailored to local conditions. Measures that could be recommended include establishing ecological pilot zones in SN areas, prioritizing the protection of grassland ecosystems in WN areas, and promoting intensive land use in the NN (northern contiguous poverty area). The present study offers a novel perspective on the interplay between the economy and the environment at the county level and achieves predictive coupling coordination through the integration of PLUS and random forest models. This investigation into coordinated urbanization–LUCC–ES development in CPAs yields valuable insights for enhancing environmental and economic well-being in similar regions within China, as well as globally.