Urbanization has an important effect on ecosystem services (ESs) and identifying the relationship between urbanization and ESs can provide a decision-making reference for regional ecological protection and management. Taking the areas along the Yellow River of Henan Province (AYRHP) as a research area, a coupling system of ESs and urbanization is established in this study to reveal the coupling relationship between the two. ESs are estimated by using Carnegie–Ames–Stanford approach, revision of universal soil loss equation, and Integrated Valuation of Ecosystem Services and Trade-offs (InVEST) models. The urbanization level is evaluated from three dimensions: population, economy, and land. The coupling coordination relationship between various ESs and urbanization in AYRHP is quantified from 2000 to 2018 on the county scale based on the coupling coordination degree (CCD) model. The lead-lag relationship between ESs and urbanization is identified by using the relative development degree model, and ecological management zoning is conducted. Results show that in the study period, net primary production (NPP), soil conservation, and food production are increased, whereas water yield is decreased. In the study period, population, economy, and land urbanization levels are increasing, and the comprehensive urbanization level is increased by 51.63%. The total CCD between NPP, food production, and water yield and comprehensive urbanization is basic or moderate coordination, whereas that between soil conservation and comprehensive urbanization is moderate maladjustment. In the research period, the coupling coordination between NPP and food production and comprehensive urbanization is increasing; that between water yield and comprehensive urbanization is fluctuated; and that between soil conservation and comprehensive urbanization is decreasing. The result of the research into the relative development degree in 2018 showed that food production, water yield, and soil conservation lag behind the urbanization level in most regions and counties along the Yellow River of Henan Province. On the basis of the lead-lag relationship between different ESs and urbanization level, the AYRHP are divided into ecological reconstruction area, ecological and agricultural improvement area, and ecological conservation area. CCD and relative development degree models can be used to evaluate the coordination relationship between ESs and urbanization, which provides scientific support for regional ES management.