Central Plains region of China, represented by Henan Province, is facing serious air pollution problems. Vehicular exhaust emissions had adverse impacts on the atmospheric environment. The first comprehensive and novel vehicle emission inventory for Henan Province using vehicle kilometers traveled, localized emission factors, and activity data at city-level was developed. Furthermore, 3 km × 3 km gridded emission and temporal variations were determined by using localized information. Results show that the total emissions of sulfur dioxide (SO2), nitrogen oxides (NOx), carbon monoxide (CO), particular matter with aerodynamic diameter < 10 μm (PM10), aerodynamic diameter < 2.5 μm (PM2.5), volatile organic compounds (VOCs), VOCs-evaporation and ammonia in 2015 were 9.1, 533.4, 1190.7, 23.7, 21.6, 150.8, 31.5 and 10.4 Gg, respectively, and the emission intensities of the above pollutants were 0.05, 2.7, 6.0, 0.1, 0.1, 0.8, 0.2 and 0.05 g/km, respectively. Vehicles meeting the Primary China 1, China 3 and China 4 contributed 89.1%, 82.7%, 75.3%, 75.5%, 75.5%, 68.2%, 68.4% and 82.3% for SO2, NOx, CO, PM10, PM2.5, VOCs, VOCs-evaporation and ammonia emissions, respectively. Zhengzhou, Zhoukou, Nanyang, Luoyang, Shangqiu and Xinyang showed relatively higher emissions and contributed more than 50% of each pollutant. The spatial distribution indicated obvious characteristics of the road network, and high-level emission was concentrated in the downtown areas. Additionally, the ozone formation potential (OFP) based on the estimated speciated VOC emissions was 569.6 Gg in Henan Province. Aliphatic and aromatic hydrocarbons were the main species of VOCs, whereas olefins contributed the largest proportion of OFP, with 42.2%.