Under the background of ecological civilization construction and targeted poverty alleviation, it is essential to understand the coupling relationship between ecosystem services and livelihood factors related to poverty alleviation in China. In this paper, 717 poverty-stricken counties in China were picked up as cases to elucidate this coupling relationship. First, we constructed evaluation index systems for ecosystem services and poverty livelihoods. Then, we calculated the coupling degree between ecosystem services and poverty livelihoods from 2000 to 2015 by using the gray coupling correlation model. Finally, we analyzed the temporal and spatial evolution of the coupling degree between ecosystem services and poverty livelihoods. The results indicate that mutual correlation degree between indicators in the ecosystem service and poverty livelihood systems was located in a range of 0.363 to 0.964. The comprehensive correlation degree of ecosystem services to poverty livelihood was 0.793, while that of poverty livelihoods to ecosystem services was 0.740. From 2000 to 2015, the coupling degrees between ecosystem services and poverty livelihoods showed "W" curve change with the values between 0.770 and 0.801. The spatial variability of coupling degree was significant, with the western region of China having the highest coupling degree and the central and eastern regions of China having lower coupling degrees. In addition, from 2000 to 2015, increasing trend of coupling degree was exhibited in 92 counties, accounting for 12.83% of all poverty-stricken counties, whereas, of all poverty-stricken counties 163 counties (22.73%) showed declining trend and 462 counties (64.44%) showed stable trend. These data rationalize that effective measures are required to lift ecosystem services out of poverty trap and into sustainable livelihoods.