It is an important way to take ecological conservation, food security and improve people's livelihood into consideration by realizing the regional sustainable development and maximizing ecosystem benefits through the dynamic changes of the trade-off and synergy relationships among multiple ecosystem services. By analyzing the changes of grain supply in county scale, and sand fixation, soil conservation and water regulation in project plots, this paper evaluated the impacts of the Grain for Green Project (GFGP) on the trade-off and synergy relationships among multiple ecosystem services. The results showed that: (1) from 2000 to 2015, food supply increased in about 76% of the project counties. Ecosystem soil conservation and water regulation functions on the GFGP plots increased in 46% and 49% of the project counties, while ecosystem sand fixation function on the GFGP plots only increased in 2% of the project counties in the wind erosion area. (2) In 1897 counties of GFGP, the significantly spatial synergy relationship between grain supply and water regulation showed in 24% counties, and between grain supply and soil conservation in 18% counties. About 38% of the counties in the wind erosion area had significantly spatial trade-off relationships between grain supply and sand fixation. (3) In addition, 31% of the GFGP counties are presented as multiple provision areas of ecosystem services, of which 43% are dual provision counties, 53% are triple provision counties, and 4% are quadruple provision counties. (4) In the past 16 years, the divergent spatial correlations between the food supply and regulation services presented as mutual transformation of trade-offs and synergies, varied change degrees of trade-offs and synergies, which reflects the importance of the joint trade-offs and synergies of multiple ecosystem services in future assessment of ecological effects for GFGP and other ecological restoration projects.