Abstract: Agricultural productive services as soft inputs in the production process offer a new path for realizing large-scale agricultural operations and improving agro-ecological efficiency by effectively integrating technology, information, and talent into agricultural production. Based on provincial panel data in China (not including Hong Kong, Macao, Taiwan and Xizang of China, the same as below) from 2005 to 2021, this study constructed a super-efficiency slack-based measure (SBM) model to measure the agro-ecological efficiency at provincial level. A kernel density map was created to analyze the temporal evolution trends in agro-ecological efficiency and to compare its differences across various regions and provinces. A two-way fixed model was used to examine the effects and mechanisms of agricultural productive services on agro-ecological efficiency. The mediating effect model was used to analyze the mediating role of farmland management scale, agricultural planting structure, and agricultural technology extension. The results showed that from 2005 to 2021, the agro-ecological efficiency of the entire country and each region showed an upward trend. China’s agro-ecological efficiency rose from 0.388 in 2005 to 0.893 in 2021. The efficiency consistently ranked as follows: eastern region > western region > central region, and major grain-sales area > major grain-production area ≈ production-sales balance area. There were significant differences in agro-ecological efficiency among the provinces (municipalities, autonomous regions). Qinghai, Shanghai, Hainan and Beijing consistently exhibited high agro-ecological efficiency, while Shanxi, Anhui, Gansu, and Jiangxi had low agro-ecological efficiency. Agricultural productivity services significantly improved agro-ecological efficiency, with results remaining valid even after endogeneity and various robustness tests. The estimation results of the intermediary effect showed that agricultural productive services improved agro-ecological efficiency by expanding the scale of farmland management, adjusting the agricultural planting structure, and promoting the extension of agricultural technologies. Compared with the eastern region, agricultural productive services in the western region had an evident effect on agro-ecological efficiency, whereas agricultural productive services in the central region showed no significant impact on agro-ecological efficiency. Compared with the major grain-producing areas, agricultural productive services in the production-sales balance areas had a profound effect on the improvement of agro-ecological efficiency. Therefore, to enhance agroecological efficiency, the agricultural production service system should be further improved by vigorously cultivating and developing specialized and diversified service entities, promoting large-scale management of agricultural land, leveraging the advantages of large-scale service operations provided by agricultural production service organizations, improving the subsidy mechanism for cultivated land protection to prevent the “non-grain” conversion of cultivated land, and improving the technological innovation of agricultural machinery and equipment by accelerating the research, development, and promotion of low-carbon and high-efficiency technologies.