Urbanization has made tremendous contributions to China's economic development since its economic reforms and opening up. At the same time, population agglomeration has aggravated environmental pollution and posed serious challenges to China's environment. This article empirically investigates the impacts of China's urbanization on eco-efficiency, comprehensively reflecting economic growth, resource input, and waste discharge. We first measured the provincial eco-efficiency in China from 2005 to 2015 using the Super Slack-Based model (Super-SBM). We then constructed a spatial model to empirically analyze the effects of urbanization on eco-efficiency at the national level, and at four regional levels. The results indicated that the regional eco-efficiency in China has fluctuated, but is generally improving, and that a gap between regions was evident, with a trend toward further gap expansion. We observed an effect of spatial spillover in eco-efficiency, which was significant and positive for the whole country, except for the western region. The influence of urbanization on China's eco-efficiency exhibited a U-curve relationship. The changing trend in the eastern, central, and western regions was the same as that in the whole country; however, the trend exhibited an inverted U-curve relationship in the northeastern region. To the best of our knowledge, covering a time period of 2005-2015, this article is the first of its kind to study the impact of urbanization on eco-efficiency in China at both the national and regional levels. This study may help policy-makers to create sustainable policies that could be helpful in balancing urbanization and the ecological environment.