Unsustainable anthropogenic activities are driving carbon emissions across the world in general and the Congo Basin of Central Africa in particular. This has led to unprecedented levels of global warming and climate change as temperatures rise, moving ever closer toward the 1.5 °C disaster threshold. The need for nature-based solutions like agroforestry has never been direr. This chapter which is based on a review of empirical literature across the Congo Basin examined the contribution of different agroforestry systems toward curbing deforestation and enhancing negative carbon emissions. Findings reveal that carbon emissions in the Congo Basin are mainly driven by the increasing conversion of forested lands into agricultural lands. Different agroforestry systems notably agrisilvicultural, silvipastoral, and agrisilvipastoral and their associated practices contribute enormously to curb deforestation by reducing pressure on natural forest ecosystems and enhance negative carbon emissions by sequestering carbon, reducing carbon emissions, and reducing the burning of fossil fuels. Pathways to harness the potential of agroforestry to reduce deforestation and enhance negative carbon emissions include integrating fast-growing tree/shrub species within agroforestry systems (bamboo, Podocarpus, Acacia), expanding the surface area covered by agroforestry systems, transitioning to an agroforestry-based bioeconomy, increasing forest tree diversity and density within agroforestry systems, factoring in agroforestry into the national determined contributions (NDCs) of Congo Basin countries, payment for ecosystem services/carbon credits to agroforestry practitioners, and crafting and implementing more agroforestry friendly policies, regulations, and legislation. Agroforestry therefore holds the key to the future as far as reducing deforestation and enhancing negative carbon emissions in the Congo Basin are concerned owing to its enormous potential to provide diverse ecosystem services while enhancing sustainability.