The Dabie Mountain area is a typical poverty-stricken area in China. It is of great significance to evaluate the ecosystem service value and its impact mechanism toward optimizing the ecological structure and coordinating ecological protection and economic development. This study determined the ecosystem service value coefficient and calculated the ecosystem service value (ESV) according to the regional economic development in the past ten years, and the ESV was spatialized based on NPP, which is closely related to ecological function. The temporal and spatial variation of ESV was then analyzed, and an RDE index was proposed to describe its response to land cover change. Further, the relationship between ESV and several parameters that reflect socioeconomic development was researched and analyzed. The results show that the total ESV in the study area first decreased and then increased, with an overall increase of CNY 3.895 billion. Among the land cover types, forest land had the greatest impact, contributing more than 70%. In the ecosystem service functions, the contribution of regulation function exceeded 50%. ESV was found to be sensitive to land cover change. On average, every 1 km2 change leads to an ESV change of about CNY 1 million. Socioeconomic-related parameters were negatively correlated with ESV, among which the correlation with per capita disposable income was the weakest, indicating that there was no obvious contradiction between human well-being and ESV. Therefore, a path for harmonious symbiotic development can be found between man and nature.