The practice of cover crops has gained popularity as a strategy to improve agricultural sustainability, but its full potential is often limited by environmental trade-offs. Using meta-analytic and data-driven quantifications of 2302 observations, we optimized cover crop practices and evaluated their benefits for global agroecosystems. Cover crops have historically boosted crop yields, soil carbon storage, and stability, but also stimulated greenhouse gas emissions. However, combining them with long-term implementation (five years or more) and climate-smart practices (such as no-tillage) can enhance these services synergistically. A biculture of legume and non-legume cover crops, terminated 25 days before planting the next crop and followed by residue mulching, is the optimal portfolio. Such optimized practices are projected to increase agroecosystem multiservices by 1.25%, equivalent to annual gains of 97.7 million metric tons in crop production, 21.7 billion metric tons in carbon dioxide sequestration, and 2.41 billion metric tons in soil erosion reduction. By 2100, the continued implementation of optimized practices could mitigate climate-related yield losses and contribute to climate neutrality and soil stabilization, especially in harsh and underdeveloped areas. These findings underscore the promising potential of optimized cover crop practices to achieve the synergy in food security and environmental protection.