Mastering the coupling and coordination relationship and driving mechanism of urbanization and ecosystem service value (ESV) is of great significance to ecological protection and regional sustainable development. In this paper, the coupling coordination model, geographic detector and GWR model are used to analyze the spatio-temporal coupling interaction between urbanization and ESV and the spatial differentiation characteristics of influencing factors from 1995 to 2018. The results of the study are as follows: (1) During the study period, cities in the Yellow River Basin experienced accelerated urban expansion, and the ESV of forests, water and wetlands increased, which offset the reduction in ESV due to the expansion of construction land and farmland and grassland. (2) The degree of coupling and coordination between the two gradually improved, but the overall situation showed a low-level coupling and coordination process. Mild coupling coordination gradually increased, reaching an increase of 38.10%; severe imbalance types tended to disappear, decreasing by 52.38%, and coupling subtypes developed from lagging urbanization to ESV backward types. The high-value areas of the coupling coordination degree are distributed in the high-value areas of ESV in the north of the upper reaches, and the low-value areas are distributed in the cities of Henan and Shandong with high urbanization levels in the downstream and most resource-based cities in the middle reaches. (3) In addition, the spatial intensity of the effect of each dominant factor on the degree of coupling coordination is different. Economic growth, technological development, environmental regulations and the proportion of forest land have positive and belt-shaped alienation characteristics for the coupling and coordination of the two, and infrastructure and temperature show negative driving characteristics. Therefore, the coupling and coordination relationship between ESV and urbanization should be clarified to help future urban planning. On the basis of determining the regional environmental carrying capacity and the adjustment direction of the rational planning of land resources, the impact of urban barriers formed by administrative boundaries and natural geographical conditions on the development of urban agglomerations should be broken to achieve the overall high-quality and coordinated development of the basin.