Here, lauric acid (LA) with a remarkable tailoring property of pore structure and porosity was adopted as modulator for the synthesis of Mn-MIL-100. Results reveal that LA amount has a significant effect on the morphology, crystal size and porous structure of prepared materials. The synthesized catalysts were coupled with a dielectric barrier discharge reactor to improve toluene decomposition performance. We found that the introduction of catalysts can remarkably enhance toluene removal efficiency (TRE), CO2/COx selectivity and energy yield (EY), and simultaneously inhibit the generation of O3 and NOx compared with the non-thermal plasma (NTP) system as the presence of catalysts with developed hierarchical porous structure and well-dispersed crystal particle provides abundant adsorbed centers and active sites for surface reactions. Amongst, LA-8 sample shows the best catalytic performance with TRE, CO2 and COx selectivity of 94.7%, 44.9% and 92.4%, respectively (specific energy density (SED) of 473 J L−1), much higher than the NTP system (respectively; 63.3%, 34.2% and 73.6%). Moreover, the EY of NTP-Catalysis system (5.19 g kWh−1) is also obviously higher than that of single NTP (1.94 g kWh−1) at SED of 262 J L−1. This work paves a way for application of MOFs in NTP-Catalysis system for VOC decomposition.