As intermediate products of photochemical reactions, alkyl nitrates (RONO2) regulate ozone (O3) formation. In this study, a photochemical box model incorporating master chemical mechanism well reproduced the observed RONO2 at an urban and a mountainous site, with index of agreement in the range of 0.66–0.73. The value 0.0003 was identified to be the most appropriate branching ratio for C1 RONO2, with the error less than 50%. Although levels of the parent hydrocarbons and nitric oxide (NO) were significantly higher at the urban site than the mountainous site, the production of C2–C3 RONO2 was comparable to or even lower than at the mountainous site, due to the lower concentrations of oxidative radicals in the urban environment. Based on the profiles of air pollutants at the mountainous site, the formation of C2–C4 RONO2 was limited by NOx (volatile organic compounds (VOCs)) when total volatile organic compounds (TVOCs)/NOx was higher (lower) than 10.0 ± 0.4 parts per billion by volume (ppbv)/ppbv. This dividing ratio decreased (p < 0.05) to 8.7 ± 0.4 ppbv/ppbv at the urban site, mainly due to the different air pollutant profiles at the two sites. For the formation of C1 RONO2, the NOx-limited regime extended the ratio of TVOCs/NOx to as low as 2.4 ± 0.2 and 3.1 ± 0.1 ppbv/ppbv at the mountainous and urban site, respectively. RONO2 formation led to a decrease of simulated O3, with reduction efficiencies (O3 reduction/RONO2 production) of 4–5 parts per trillion by volume (pptv)/pptv at the mountainous site and 3–4 pptv/pptv at the urban site. On the other hand, the variations of simulated O3 induced by RONO2 degradation depended upon the regimes controlling O3 formation and the relative abundances of TVOCs and NOx.