Radiocarbon can be used to trace fossil fuel CO2 (CO2ff) in the atmosphere, because radiocarbon has been depleted in fossil fuels. Here we present our study on the spatial distribution and temporal variations of CO2ff in Xi'an City, China using D14C of both green foxtail (Setaria viridis, L. Beauv.) leaf samples and urban air samples collected in the recent years. Our results show that the CO2ff indicated by green foxtail ranged from 14.7 ± 1.7 to 52.6 ± 1.7 ppm, reflecting high CO2ff mole fractions in downtown, industrial areas, and at road sites, and low CO2ff mole fractions in public parks. Meanwhile, the monthly CO2ff reflected by air samples showed higher value in winter (57.8 ± 17.1 ppm) than that in summer (20.2 ± 9.8 ppm) due to the enhancement usage of coal burning and the poor dispersion condition of atmosphere. This study displays that the increased fossil fuel emission is associated with the fast development of Xi'an City in China. It is worth mentioning that the green foxtail samples can be used to map out the CO2ff spatial distribution on large scale quickly and conveniently, while the air samples can be used to trace the CO2ff temporal variations with high resolution effectively. Therefore the D14C of both green foxtail and air samples is a good indicator of CO2ff emission.