Generally, porous carbon nanospheres materials are usually prepared via a template method, which is a multi-steps and high-cost strategy. Here, we reported a porous carbon nanosphere solid acid with high surface area and superior porosity, as well as uniform nanospheical morphology, which prepared by a facile chemical activation with ZnCl2 using resorcinol-formaldehyde (RF) resins spheres as precursor. The activation of RF resins spheres by ZnCl2 at 400°C brought high surface area and large volume, and simultaneously retained numerous oxygen-containing and hydrogen-containing groups due to the relatively low processing temperature. The presence of these functional groups is favorable for the modification of –SO3H groups by a followed sulfonation treating with sulphuric acid and organic sulfonic acid. The results of N2 adsorption–desorption and electron microscopy clearly showed the preservation of porous structure and nanospherical morphology. Infrared spectra certified the variation of surface functional groups after activation and the successful modification of –SO3H groups after sulfonation. The acidities of catalysts were estimated by an indirect titration method and the modified amount of –SO3H groups were examined by energy dispersive spectra. The results suggested sulfonated porous carbon nanospheres catalysts possessed high acidities and –SO3H densities, which endowed their significantly catalytic activities for biodiesel production. Furthermore, their excellent stability and recycling property were also demonstrated by five consecutive cycles.