Knowledge of vertical CO2 distribution is important for development of CO2 transport models and calibration/validation of satellite-borne measurements. In this study, vertical profiles of CO2 concentration within 0-1000 m were measured using a tethered balloon at a suburban site in Xiamen, which is undergoing fast urbanization. The characteristics of CO2 vertical distribution were investigated under both stable and convective boundary-layer conditions. The correlation of ground level CO2 concentrations and those at high altitudes decreased with altitude and show significant correlation in the first 300 m with R=0.78 at 100 m, R=0.52 at 200 m, R=0.40 at 300 m (P<0.01). The correlation keeps almost constant for 300-800 m, and there is no obvious correlation at 800 m, indicating that the impact of ground level CO2 was restricted within the 300 m above the ground. When comparing the vertical profiles obtained at different times during a 24 h period, it was found that CO2 concentration exhibited more obvious diurnal pattern at surface level than at high altitude because of the variation of sources and sinks of CO2 at ground level. Most profiles demonstrated declining trends of CO2 concentration with increasing altitude. The vertical profiles of CO2 were fitted to obtain an empirical equation for estimating CO2 vertical concentration in the lower atmosphere (0-1000 m): y=-75.04+1.17×109e-x/28.01, R2=0.59 (P<0.05). However, for some cases opposite patterns were observed that the CO2 concentration profiles showed a turning point at a certain altitude or little variation with altitude under certain meteorological conditions. The atmospheric boundary layer depth and atmospheric stability are two major factors controlling the vertical structure of CO2 profile. The results would improve our understanding of the spatial and temporal variation of CO2 in urban environment, which would facilitate using 3-D transport model to study the impacts of CO2 on urban environment.