Recently, atmospheric ozone pollution has demonstrated an aggravating tendency in China. To date, most research about atmospheric ozone has been confined near the surface, and an understanding of the vertical ozone structure is limited. During the 2016 G20 conference, strict emission control measures were implemented in Hangzhou, a megacity in the Yangtze River Delta, and its surrounding regions. Here, we monitored the vertical profiles of ozone concentration and aerosol extinction coefficients in the lower troposphere using an ozone lidar, in addition to the vertical column densities (VCDs) of ozone and its precursors in the troposphere through satellite-based remote sensing. The ozone concentrations reached a peak near the top of the boundary layer. During the control period, the aerosol extinction coefficients in the lower lidar layer decreased significantly; however, the ozone concentration fluctuated frequently with two pollution episodes and one clean episode. The sensitivity of ozone production was mostly within VOC-limited or transition regimes, but entered a NOx-limited regime due to a substantial decline of NOx during the clean episode. Temporary measures took no immediate effect on ozone pollution in the boundary layer; instead, meteorological conditions like air mass sources and solar radiation intensities dominated the variations in the ozone concentration.