The phosphorus-doped macroporous carbon spheres (PMCS) with a high specific surface area (574.68 m² g⁻¹) were synthesized by a template method. A series of catalytic experiments showed that the PMCS possessed excellent catalytic ability for the selective oxidation of cyclooctene (conversion based on cyclooctene was 50.69% and the selectivity to epoxycyclooctane was 88.47%).