Metal-free catalysts have been proved to be a low-cost and environmentally friendly species in aerobic oxidative desulfurization (ODS). In this work, exfoliated metal-free boron carbide with few-layered structure, small size, and abundant defects, was first employed in an aerobic ODS system for ultra-deep desulfurization. The exfoliation process was realized by employing a planetary ball mill strategy. Detailed characterizations showed that the ball milling process not only induces thinner layers and small sizes but also introduces numerous defects into the boron carbide catalysts, which is vital in metal-free catalysis. Furthermore, the exfoliated boron carbide catalyst was applied in aerobic ODS system, and 99.5 % of sulfur removal was obtained. Moreover, the catalyst can be recycled 17 times without a significant decrease in catalytic activity. In particular, it was found that ∼90 % of the sulfur compounds in real diesel oil could be removed by the current aerobic ODS system.