Abstract: A series of basic nitrogen doped carbon hollow spheres (p-N-C) catalysts derived from waste tires were prepared by a green, facile and environmental “leavening” strategy for the catalytic oxidation of pentanethiol. Compared to pristine carbon, the p-N-C has a higher surface curvature conducive to the enrichment of substrates, leading to an excellent catalytic performance. This increased surface curvature of p-N-C was fabricated on the synergistic effect of two foaming agents ((NH4)2C2O4 and NaHCO3), and the released gas also endows the spherical shell of p-N-C with a hierarchical porous structure, promoting the accessibility of active sites with pentanethiol. Pyridine-like and pyrrolic-like nitrogen atoms were investigated as reactive sites on the p-N-C to accelerate the electron transfer from sulfur to active surface oxygen and enhance the adsorption/oxidation process. As a result, the optimal p-N-C catalyst exhibits superior adsorption and oxidation performance (99.9%) of pentanethiol, outperforming the “unleavened” catalyst (20.8%). This work offers a new avenue for the fabrication of highly efficient materials for the desulfurization of fuel.