According to the survey data on land use changes obtained from the Department of Land and Resources of Anhui Province and the national ecosystem service values of various types of land units in 2013, we estimated the ecosystem service values of Anhui in 2005, 2009, and 2013 and analyzed its structure and spatiotemporal features. We found that the ecosystem service values of Anhui in 2005, 2009, and 2013 were 384.6055, 378.8165, and 375.4096 billion yuan, respectively. During the study period, the rank of each ecosystem service function value and the rank of contribution of individual land use types to the regional ecosystem service values were not changed. The main reason for the decline of regional ecosystem service value was the reduction of wetland area, water area, cultivated land, and grassland. The ecosystem stability of Lu'an, Anqing, Xuancheng, Huangshan, Chuzhou, Hefei, and Chizhou has been playing a decisive role in maintaining the quality of ecological environment in Anhui province. The quality of regional ecological environment showed a zonal distribution pattern.