<p><strong>Abstract.</strong> PM<sub>2.5</sub>, a particulate matter with a diameter of 2.5 micrometers or less, is one of the major components of the air pollution in eastern China. In the past few years, China's government made strong efforts to reduce the PM<sub>2.5</sub> pollutions. However, another important pollutant (ozone) becomes an important problem in eastern China. Ozone (O<sub>3</sub>) is produced by photochemistry, which requires solar radiation for the formation of O<sub>3</sub>. Under heavy PM<sub>2.5</sub> pollution, the solar radiation is often depressed, and the photochemical production of O<sub>3</sub> is prohibited. This study shows that during fall in eastern China, under heavy PM<sub>2.5</sub> pollutions, there were often strong O<sub>3</sub> photochemical productions, causing a co-occurrence of high PM<sub>2.5</sub> and O<sub>3</sub> concentrations. This co-occurrence of high PM<sub>2.5</sub> and O<sub>3</sub> is un-usual and is the main focus of this study. Recent measurements show that there were often high HONO surface concentrations in major Chinese mega cities, especially during daytime, with maximum concentrations ranging from 0.5 to 2&#8201;ppbv. It is also interesting to note that the high HONO concentrations were occurred during high aerosol concentration periods, suggesting that there were additional HONO surface sources in eastern China. Under the high daytime HONO concentrations, HONO can be photo-dissociated to be OH radicals, which enhance the photochemical production of O<sub>3</sub>. In order to study the above scientific issues, a radiative transfer model (TUV; Tropospheric Ultraviolet-Visible) is used in this study, and a chemical steady state model is established to calculate OH radical concentrations. The calculations show that by including the OH production of the photo-dissociated of HONO, the calculated OH concentrations are significantly higher than the values without including this production. For example, by including HONO production, the maximum of OH concentration under the high aerosol condition (AOD&#8201;=&#8201;2.5) is similar to the value under low aerosol condition (AOD&#8201;=&#8201;0.25) in the no-HONO case. This result suggests that even under the high aerosol condition, the chemical oxidizing process for O<sub>3</sub> production can occurred, which explain the co-occurrence of high PM<sub>2.5</sub> and high O<sub>3</sub> in fall season in eastern China. However, the O<sub>3</sub> concentrations were not significantly affected by the appearance of HONO in winter. This study shows that the seasonal variation of solar radiation plays important roles for controlling the OH production in winter. When the solar radiation is in a very low level in winter, it reaches the threshold level to prevent the OH chemical production, even by including the HONO production of OH. This study provides some important scientific highlights to better understand the O<sub>3</sub> pollutions in eastern China.</p>