Sorbent with a great quantity of highly dispersed active components is of importance to achieve excellent desulfurization performance. Thus, Zn@MnOx/porous carbon nanofibers (PCNFs) sorbent has been constructed via electrospinning, carbonization and hydrothermal techniques in this study. The as-prepared sorbent realizes a sulfur capacity of 9.63 g S 100 g−1 sorbent and a utilization 117% of ZnO, which can be attributed to the synergetic effects of the enlarged surface area of PCNFs and the uniformly distributed active components. The specific surface area of modified PCNFs is nearly five times higher than that of the pristine CNFs, providing larger loading area and more attachment sites for metal oxides. Activation with KMnO4 not only generates active component MnOx but also presets ‘seed’ for the attachment of Zn2+, which is beneficial for the high dispersion of active components. The presented method is beneficial to producing sorbents with better structure and promotes desulfurization performances.