In recent decades, the BRICS countries have experienced rapid economic growth, much of which has been driven by agriculture, natural resource extraction, and industrial exports. However, the continued expansion of these sectors is accompanied by growing environmental vulnerabilities. While value addition in agriculture, forestry, and fishing is crucial for development, it is also widely acknowledged as a contributor to land degradation. Against this backdrop, this study examines the impact of agriculture, forestry, and fisheries value added on environmental performance in the BRICS countries over the period of 1990–2023. This study is the first to integrate agricultural, forestry, and fishing (AFF) value added, natural resource rents, green innovation, environmental policy stringency, and greenhouse gas (GHG) emissions into a single framework, with an emphasis on the BRICS countries. We employ quantile regression to uncover how these relationships differ across different levels of the distribution of GHG emissions. As a robustness check, we use the bootstrap quantile regression approach, which estimates coefficients and standard errors through a bootstrapping procedure. The results show that primary sector value addition is positively related to GHG emissions. However, renewable energy consumption, environmental policy stringency, total natural resource rents, and green innovation negatively affect GHG emissions.