During a field study in southern Africa (Southern African Fire-Atmosphere Research Initiative (SAFARI-92)), black carbon formation was quantified in the residues of savanna fires. The volatilization ratios of C, H, N, and S were determined by measuring their contents in the fuel and residue loads on six experimental sites. The volatilization of sulfur (86 ± 8%) was significantly higher than previously reported. Volatilization of H, N, and S was significantly correlated with that of carbon, enabling us to estimate their volatilization during savanna fires by extrapolation from those of carbon. By partitioning the residues in various fractions (unburned, partially burned, and ash), a strong correlation between the H/C ratio in the residue and the formation of black carbon was obtained. The ratio of carbon contained in ash to carbon contained in the unburned and partially burned fraction is introduced as an indicator of the degree of charring. As nitrogen was enriched in the residue, especially in the ash fraction of >0.63 mm, this indicator may be useful for an assessment of nutrient cycling. We show that the formation of black carbon is dependent on the volatilization of carbon as well as the degree of charring. The ratio of black carbon produced to the carbon exposed to the fire in this field study (0.6–1.5%) was somewhat lower than in experimental fires under laboratory conditions (1.0–1.8%) which may be due to less complete combustion. The average ratio of black carbon in the residue to carbon emitted as CO2 ranged from 0.7 to 2.0%. Using these ratios together with various estimates of carbon exposed or emitted by savanna fires, the worldwide black carbon formation was estimated to be 10–26 Tg C yr−1 with more than 90% of the black carbon remaining on the ground. The formation of this black carbon is a net sink of biospheric carbon and thus of atmospheric CO2 as well as a source of O2.