This study aimed to put forward a strategy to synthesize cobalt/N-Doped carbon hollow spheres (Co/NCHPs) with ample reactive sites. The zeolitic imidazolate framework-67 was loaded on the polystyrene nanosphere (PS@ZIF-67) as precursors, followed by a controlled pyrolysis to obtain Co/NCHPs with a large single hole on each sphere. The 1O2, SO4•−, O2•−, and •OH were identified as the main reactive oxygen species (ROSs) by electron paramagnetic resonance (EPR) experiments. It is also worth noting that electron transfer was also the main non-radical pathway for tinidazole (TNZ) degradation in Co/NCHPs/PMS systems. The effects of reaction conditions on TNZ degradation were investigated. 20 mg/L of TNZ was degraded within 6 min under UV–visible light irradiation. Besides, the degradation efficiency of four organic pollutants was higher than 95 % in different water matrices. Moreover, Co/NCHPs exhibited an exceptional photocatalytic performance for several antibiotics and organic dyes mixed solution in natural water. Furthermore, the recycling test of Co/NCHPs indicated that catalysts can be reused five times without obvious activity loss. This work provided a facile and large-scale preparation method to obtain Co/NCHPs.