Nitrogen oxides (NOx ≡ NO + NO2 ) are of central importance for air quality, climate forcing, and nitrogen deposition to ecosystems. The Geostationary Environment Monitoring Spectrometer (GEMS) is now providing hourly NO2 satellite observations over East Asia, offering the first direct measurements of NO2 diurnal variation from space to guide understanding of NOx emissions and chemistry. The NO2 retrieval requires independent vertical profile information from a chemical transport model (CTM) to compute the air mass factor (AMF) that relates the NO2 column measured along the line of sight to the NO2 vertical column. Here, we use aircraft observations from the Korea-United States Air Quality (KORUS-AQ) campaign over the Seoul metropolitan area (SMA) and around the Korean Peninsula in May–June 2016 to better understand the factors controlling the NO2 vertical profile, its diurnal variation, the implications for the AMFs, and the ability of the GEOS-Chem CTM to compute the NO2 vertical profiles used for AMFs. Proper representation of oxidant chemistry is critical for the CTM simulation of NO2 vertical profiles and is achieved in GEOS-Chem through new model developments, including aerosol nitrate photolysis, reduced uptake of hydroperoxy (HO2 ) radicals by aerosols, and accounting for atmospheric oxidation of volatile chemical products (VCPs). We find that the tropospheric NO2 columns measured from space in the SMA are mainly contributed by the planetary boundary layer (PBL) below 2 km altitude, reflecting the highly polluted conditions. Repeated measurements of NO2 vertical profiles over the SMA at different times of day show that diurnal change in mixing depth affecting the NO2 vertical profile induces a diurnal variation in AMFs of comparable magnitude to the diurnal variation in the NO2