The soil carbon saturation concept suggests an upper limit to store soil organic carbon (SOC), set by the mechanisms that protect soil organic matter from decomposition. Biochar has the capacity to protect new C including rhizodeposits and microbial necromass. However, the decadal scale mechanisms by which biochar influences the molecular diversity, spatial heterogeneity, and temporal changes of SOC persistence remain unresolved. Here we show that the soil C saturation ceiling of a Ferralsol under subtropical pasture could be elevated by 2 Mg (new) C ha-1 by the application of Eucalyptus saligna biochar 8.2 years after the first application. Using one, two-, and three-dimensional analyses, significant increases were observed in the spatial distribution of root-derived 13C in microaggregates (53-250 µm, 11 %) and new C protected in mineral fractions (<53 µm, 5 %). Microbial C-use efficiency was concomitantly improved by lowering specific enzyme activities, contributing to the decreased mineralization of native SOC by 18 %. We provide evidence that the global SOC ceiling can be elevated using biochar in Ferralsols by 0.01-0.1 Pg new C yr-1.