AbstractUmbric ferralsols (UF) have organic carbon stocks within the first 1 m of soil profile depth that are nearly double the size (~19 kg C m−2) compared to the average carbon stocks of all other ferralsols (~10 kg C m−2). Here, we investigate processes that allow UF to gain and maintain such extraordinary carbon stocks. Using the International Soil Research and Information Center database, complemented with recently published datasets, we show that the carbon saturation capacity of the clay + silt fractions in UF (22.8 ± 5.7 g C kg−1 soil, n = 59) does not exceed the carbon saturation capacity in other ferralsols (23.3 ± 6.2 g C kg−1 soil, n = 165), thus eliminating a particularly retentive mineral matrix as a possible explanation. Rather, carbon stocks were correlated with the thickness of A horizons (106 ± 49 cm, n = 59 in umbric versus 35 ± 22 cm, n = 165 in non‐umbric ferralsols). We subsequently hypothesized that differences in A‐horizon thickness arose from two pedogenic scenarios: (i) superior carbon accrual resulting from a unique vegetation cover capable of allocating large quantities of carbon to belowground plant organs; and (ii) geomorphic processes that led to carbon burial. We evaluated the plausibility of these scenarios considering landscape history and associated carbon flux rates, hillslope position, as well as δ13C values and Ti/Zr ratios for subsets of ferralsol profiles studied by us in a region that encompasses latitudes from 26 to 7°S in eastern Brazil. We found that exceptional carbon stocks were most prevalent in the gradual transition zone (ecotone) between savanna and rainforest, likely resulting from erosion–deposition processes, historic changes of vegetation cover composed of grasses and arboreal elements, and active bioturbation. We suggest that attempts to sequester carbon in non‐umbric ferralsols will be most successful if they emulate or promote the biotic and abiotic processes prevalent in the savanna/rainforest ecotone.