Achieving excellent efficiency to mineralize volatile organic compounds (VOCs) under nonthermal plasma catalysis (NTP-catalysis) systems tremendously relies on the catalyst design. Herein, we report a dual-template strategy for synthesizing a core− shell structured nitrogen-enriched hollow hybrid carbon (N-HHC) by a facile pyrolysis of a Mn-ZIF-8@polydopamine core−shell precursor. N-HHC exhibits a remarkable plasma synergy effect and superior degradation efficiency for toluene (up to 90% with a specific input energy of 281 J/L), excellent CO 2 selectivity (>45%), and byproduct-inhibiting capability. Such outstanding functionality of the developed N-HHC is uniquely attributed to its hollow multistage and channeling structure, high concentration of O 3 -decomposing species (pyrrolic and oxide pyridinic-N), and abundant ZnO active sites. Shedding light on an efficient synthetic strategy for designing an advanced nanocatalyst with enhanced VOC destruction in the NTP-catalysis system, the present results could be extended to design other N-doped metal/metal oxide-decorated hollow porous carbons for environment-related applications.