Understanding the coupling relationship between ecosystem services and poverty livelihoods is a prerequisite for poverty eradication and ecological protection in China. In this paper, we intended to quantify the coupling relationship between ecosystem services and poverty livelihoods in 717 poverty-stricken counties in China. First, we identified distinct levels of ecosystem services and poverty respectively in the poverty-stricken areas based on the ecosystem services subsystem index and poverty livelihoods subsystem index. Then, we calculated the coupling degree and coupling coordination degree between the ecosystem services and the poverty livelihoods in China’s poverty-stricken counties from 2000 to 2015. Finally, we analyzed the temporal and spatial evolution of the coupling between ecosystem services and poverty livelihoods. The results indicate that the ecosystem services showed a trend of first decreasing and then increasing, while the poverty level showed an increased trend. In addition, the coupling relationship between ecosystem services and poverty livelihoods in poverty-stricken counties was also improved from 2000 to 2015. However, the coupling degree value or coupling coordination degree values in some counties or contiguous impoverished areas showed a decreased trend, the coupling relationship between ecosystem services and poverty livelihoods in those counties or areas was higher conflict. Future more, the coupling relationship in China’s poverty-stricken counties was mainly intermediate conflict and low conflict, which need to improve in the future. Thus, it is suggested that effective measures are required to lift ecosystem services out of the poverty trap and into sustainable livelihoods.