The study of the coupling and coordination relationship between urbanization and ecosystem services as a bridge connecting the natural environment with the social economy has received widespread attention. Selecting 333 cities in China, we calculated the urbanization level and ecosystem service capacity with the integrated evaluation index in 2010 and 2015. At the same time, the temporal and spatial evolution characteristics of the urbanization level and ecosystem service capacity were analyzed, and the spatial econometric model was used to explore the relationship between ecosystem services and urbanization. The study found that: (1) the urbanization level of the cities shows the spatial pattern of "East High-West Low, and South High-North Low". The average value increased from 0.0792 in 2010 to 0.0987 in 2015, which increased by 24.62%. Most cities are still in the preparation development stage, while only Shanghai and Shenzhen have entered a highly developed stage. (2) The urban ecosystem service capacity shows a "Southeast High-Northwest Low" spatial pattern, whose average value increased from 0.2542 in 2010 to 0.2621 in 2015, with an increasing of 3.11%. But the average value of 81 cities dropped from 0.1201 in 2010 to 0.1183 in 2015, with a decreasing of 1.50%, which have formed a spatial aggregation feature of the significant deterioration. (3) By the Spatial Error Model, the regression coefficients of the score of integrated urbanization, population urbanization, land urbanization, and economic urbanization are -0.1303, -0.2019, -0.2404, and 0.1946, respectively. Economic development has become a powerful tool for improving ecosystem services. Finally, we suggest that the coordinated management of ecological space should be strengthened; the inter-regional economic cooperation development mechanism needs to be established; and the population growth, land construction, and economic development should be coordinated.