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Diesel particulate and NOx reduction system (DPNR) is an effective technology for the diesel after-treatment system, which can reduce particulate matter (PM) and nitrogen oxides (NOx) simultaneously. Further improvement of the DPNR is expected for cleaner air in the future. The catalyst for the DPNR (called DPNR catalyst) consists of a NOx Storage Reduction (NSR) catalyst coated onto a Diesel Particulate Filter (DPF). The development of the DPNR catalyst for the decrease of exhaust weight has been considered before now with respect to the PM combustion. But it will be necessary to focus on PM particle number emissions in the future. In this study, the relationship between the pore structure of the DPNR catalyst and the trapping of PM to lower particle number was clarified by evaluating a high-porosity, large-pore cordierite DPF with an average pore size of 20 μm or greater. Furthermore, the optimal pore structure to trap PM particles in a highly effective manner was discussed.