Ecosystem service value (ESV) encapsulates the benefits that ecosystems confer upon humans, serving as an indicator of regional ecosystem quality. Henan Province (HNP) is undergoing substantial land use transformations, which are unique in China in that they span four river basins – the Huaihe River Basin (HUB), Yellow River Basin (YEB), Yangtze River Basin (YZB), and Haihe River Basin (HAB). This study uniquely explores the spatiotemporal evolution of changes in land use and ESV across four major river basins. Our findings reveal significant variations in ESV among different river basins. The spatial distributions of the land use categories varied across the four river basins, with distinct trends in the ESVs. Construction land exhibited the most pronounced changes. The forest and water ESVs initially declined but later recovered, whereas the cropland and grassland ESVs consistently decreased. The ESV related to land use in HNP increased by 9.96 billion CNY during this period, with high ESV areas located at the junction of YEB, YZB, HUB, and southern HUB. Synergistic relationships dominate ESV interactions, particularly in Regulating Services (RS), Supporting Services (SS), and Cultural Services (CS), whereas trade-offs are more prevalent in Provisioning Services (PS). Spatially, ESV hot spots are concentrated in YZB, whereas the cold spots are located primarily in HUB and HAB. Over time, the ESV disparities among the four river basins have intensified. This research enhances methodologies for quantifying river basins’ ESV, providing vital support for land resource management, ecological conservation, and high-quality development in major river basins in HNP, China. These findings will inform policymaking for sustainable basin ecosystem development.