Abstract Since the photolysis rate plays an important role in any photoreaction leading to compound sink and radical formation/destruction and eventually O3 formation, its impact on the simulated O3 concentration was evaluated in the present study. Both RADM2 and RACM were adopted with and without updated photolysis rate constants. The newly developed photolysis rates were determined based on two major absorption cross-section and quantum yield data sources. CMAQ in conjunction with meteorological MM5 and emission data retrieved from Taiwan and East Asia were employed to provide spatial and temporal O3 predictions over a one-week period in a three-level nested domain [from 81 km × 81 km in Domain 1 (East Asia) to 9 km × 9 km in Domain 3 (Taiwan)]. Four cases were analyzed, namely, RADM2, with the original photolysis rates applied in Case 1 as a reference case, RADM2, with the updated photolysis rates applied in Case 2, and RACM, with and without the updated photolysis rates applied in Cases 3 and 4, respectively. A comparison of the simulation and observed results indicates that both the application of updated photolysis rate constants and RACM instead of RADM2 enhanced all three error analysis indicators (unpaired peak prediction accuracy, mean normalized bias error and mean absolute normalized gross error). Specifically, RADM2 with the updated photolysis rates resulted in an increase of 12 ppb (10%) in the daily maximum O3 concentration in southwestern Taiwan, while RACM without the updated photolysis rates resulted in an increase of 20 ppb (17%) in the daily maximum O3 concentration in the same area. When RACM with the updated photolysis rate constants was applied in the air quality model, the difference in the daily maximum O3 concentration reached up to 30 ppb (25%). The implication of Case 4 (RACM with the updated photolysis rates) for the formation and degradation of α-pinene and d-limonene was examined.