In this study, the ordered mesoporous jar structure ZnO particles have been synthesized by template method. The cetyltrimethylammonium bromide (CTMAB) was used as the template agent, and zinc acetate dihydrate was used as zinc sources. The prepared material has ordered mesoporous on the surface. The prepared ordered mesoporous ZnO particles showed the hexagonal prisms hollow jar structure, the hexagonal prisms average diameter was about 150 nm, the average length was about 200 nm, and the jar average diameter was about 100 nm. The prepared materials were used as a gas sensor to test the toxic gas. The ordered mesoporous ZnO material showed more excellent gas sensing performances than the imporous ZnO material which was prepared without template agent by the same method. In particular, the ordered mesoporous ZnO showed a higher response to NOx, the detection limit reached to 0.5 ppm, the sensitivity reached to 66.92, and the response time was 1.08 s to 100 ppm NOx at 193 °C. The prepared material will be an excellent gas sensing matrix materials, and have a wide application prospect in gas sensors field.