Transition metal and nitrogen co-doped carbon materials (M–N–C) have attracted great attention in the field of catalysis due to their high atomic utilization and outstanding catalytic performance. Herein, a series of Co and N-doped carbon catalysts (Co–N-C@mSiO₂-x) were successfully prepared by pyrolysis of cobalt porphyrins in situ synthesized in the cavity of mesoporous hollow silica spheres according to a ship-in-bottle method. The optimal catalyst exhibited excellent catalytic performance for the selective oxidation of ethylbenzene, with 95.5% conversion for ethylbenzene and 98.9% selectivity toward acetophenone. In combination with characterization techniques, acid treatment experiments and KSCN poisoning tests, the successful synthesis of cobalt-porphyrins in hollow silica spheres was demonstrated, and the excellent performance of Co–N-C@mSiO₂-0.10 was attributed to the more acid-resistant Co–N_x species as the main metal active center. In addition, the N-containing groups could significantly facilitate the conversion of ethylbenzene. This work is expected to provide a straightforward and green approach to design metal and N co-doped carbon materials.