Productivity in smallholder farming systems is low due to the high levels of soil degradation, nutrient depletion, and climate variability, all of which threaten food security and rural livelihoods. Corrective measures like amending soils with biochar and biofertilizers have been suggested for their ability to enhance soil health, increase crop productivity, and improve resilience of the farming systems. This chapter integrates evidence on the synergistic potential of biochar and biofertilizer co-application in African farming systems. When co-applied, the two amendments interact in ways that amplify microbial activity, nutrient retention, and plant resilience, resulting in improved yields and carbon sequestration. This chapter explores the mechanisms underpinning this synergy, including the effects on soil structure, microbial habitats, water retention, and greenhouse gas mitigation. Additionally, this chapter assesses the economic feasibility, scalability, and sustainability of adopting biochar–biofertilizer systems across diverse African agroecosystems.