In light of the tremendous pressure for improving urbanization levels and expanding construction land on ecosystems, regional sustainable development is premised on the coordinated development of the ecological environment and urbanization. This paper focuses on the Circum-Bohai-Sea Region and assesses the ecosystem service value (ESV) and urbanization level using the equivalence factor and entropy-weighted TOPSIS methods. Based on these assessments, it examines the coupling coordination between the ESV and urbanization as well as the obstacles to this coordination, utilizing the coupling coordination degree model, spatial autocorrelation model, and obstacle model. The results revealed several key findings. First, the Circum-Bohai-Sea Region experienced a continuous improvement in the urbanization level from 2005 to 2020, which presented a “center–periphery” spatial pattern. Overall, the ESV exhibited an N-shaped trend, namely, initially increasing, then decreasing, and then rapidly increasing. The ESV per unit of area exhibited a spatial difference, with the boundary of Baoding and Cangzhou as the dividing line. The ESV per unit of area in the northern parts was higher than that in the southern parts. Second, the degree of the coupling coordination between the ESV and urbanization exhibited an inverted U-shaped trend, initially increasing and then slightly decreasing. It also exhibited significant spatial heterogeneity, with the degree of the coupling coordination in the northern parts being higher than that in the southern parts and that in the central parts being higher than those in the eastern and western parts. Additionally, the ESV showed a significant spatially positive correlation with urbanization. H-H clusters were predominantly found in central and southern Liaoning Province, while L-L clusters were primarily located in southern Hebei Province and western Shandong Province. Third, the obstacle factors remained stable during the study period. The top five obstacles in the ESV system were the water resource supply, nutrient cycling maintenance, raw material production, aesthetic landscape, and food production. Moreover, the top five obstacles in the urbanization system were the number of college students per 10,000 people, population density, number of health technical personnel per 10,000 people, per capita road area, and proportion of secondary and tertiary industry output values.