Despite the potential of agroecological practices to promote sustainable agrifood systems, their adoption among farmers is limited, and there is insufficient information regarding their impact on farm performance. This study evaluates the adoption of agroecological practices and their impact on farm performance among vegetable farmers in Botswana. The multivariate probit model was used to understand the complementarity and/or substitutability of the key agroecological practices under consideration—mulching, cover cropping, afforestation, and minimum tillage, as well as their determinants. Furthermore, the direct two-stage least squares (direct-2sls) technique within the framework of instrumental variable treatment effect regression (ivtreatreg) was used to eliminate self-selection bias that may be evident as a result of observed and unobserved characteristics. The results indicated that the agroecological practices are complementary and that the practice of one agroecology is conditional on another. The factors shaping the adoption of these agroecological practices vary among them. Furthermore, the adoption of agroecological practices led to a significant improvement in farmers' net revenue and yield, and farmers that did not adopt any of the practices would have been better off if they had adopted them. These findings have significant implications for stakeholders and will boost the campaign for the adoption of agroecological practices to improve farm performance and, consequently, farmers' welfare.