Urbanization in China has entered a stage that urban agglomerations are the major urbanization mode. As the extensive economic growth mode did not change fundamentally, the ecological problems during the urbanization process have become increasingly prominent. Based on the land use/land cover change in 1995, 2005 and 2015, we measured the spatiotemporal distribution features of the ecosystem services value (ESV) in the middle reaches of the Yangtze River Urban Agglomerations (MRYRUA). In addition, we investigated the spatial relationship between ecosystem services value and urbanization by using the bivariate Moran's I methods, the ordinary least squares method, and the spatial regression models. The results showed that: (1) the ESV during the study period in the MRYRUA decreased significantly, while the urbanization level increased significantly, exhibiting opposite spatial distribution features; (2) there was significant spatial dependence between average ESV and urbanization level in the MRYRUA; (3) the spatial regression model was proved to be more suitable for measuring the spatial interaction between ESV and urbanization level. The development of urbanization would lead to the decline of ESV, and there was a U-shaped curve relationship between them. The ESV is influenced not only by the individual elements, but also by neighboring elements or even further elements. The spatial dependence effect and spatial spillover effect between ESV and urbanization level should be fully considered to implement cross-regional joint governance in the future land use planning and ecosystem protection planning.