While catalyst morphology plays an essential role in traditional thermal catalysis, the specific effects in plasma catalysis deserve further in-depth study. In the present study, hollow NiO nanospheres with a rambutan-like structure were successfully prepared by MOFs-derived method involving morphology modulation, and employed for the in-plasma catalytic oxidation of benzene. The results show an enhancement of 60 % for benzene removal, while CO2 selectivity was increased by 20 %. The energy consumption for 95 % benzene removal efficiency (RE95%) was also reduced from 3600 J/L to 1100 J/L. Specifically, the hollow spherical shell structure is more abundant in surface oxygen species, including chemisorbed oxygen and surface lattice oxygen, which can be activated by plasma; the hollow structure also modulates the plasma discharge by shielding effect. The plasma field in turn also excites the oxidation activity of NiO, thus achieving the synergistic effect. In addition, a more comprehensive benzene decomposition pathway is proposed by analysis of the gaseous and non-gaseous intermediates (tar), where the plasma non-selectively breaks the chemical bonds of reactants and the catalyst selectively oxidizes the organic intermediates to CO2, and they promote each other to achieve synergistic effects.