Research on ecosystem services and residents’ well-being in old revolutionary base areas is an important task for China’s ecological civilization construction and rural revitalization. Taking Jinzhai County, the core area of Dabie Mountains, China, as an example, based on InVEST model, the methods of spatial autocorrelation and coupling coordinated development degree, the spatiotemporal evolution, spatial heterogeneity and coupling association patterns of ecosystem services and multidimensional well-being in the study area from 2005 to 2020 were discussed. The major results are: In the past 15 years, in the core area of the Dabie Mountains, ecosystem services such as food supply, soil retention and water yield showed an upward trend, carbon sequestration and biodiversity maintenance showed a downward trend. The comprehensive index of multidimensional well-being in the core area of Dabie Mountain increased by 27.23% and the spatial difference in multidimensional well-being is gradually narrowing. By the analysis of coupling coordination, the number of units with the type of coupling disharmony between ecosystem services and multidimensional well-being in the study area decreased significantly from 56.85% in 2005 to 26.81% in 2020, respectively. The analysis of geographical detection showed that the habitat quality factor was the dominant controlling factor of coupling coordination spatial difference. By bivariate spatial autocorrelation analysis, in the past 15 years, the number of units with the “high ecology-high well-being” synergy type increased from 5.44% to 13.31%. The results can provide a reference for accurate identification, optimal regulation and synergistic improvement between ecosystem services and relative poverty in the Dabie Mountain area.