Accurate simulation of volatile organic compound (VOC) emissions and their role in ozone (O₃) formation remains a persistent challenge in chemical transport models (CTMs). Most models rely on lumped surrogate species, limiting their ability to represent speciated VOCs and directly compare with observations. In this study, we develop an enhanced version of the Community Multiscale Air Quality model, termed CMAQ-PAMS, which explicitly incorporates 54 VOC species targeted by the Photochemical Assessment Monitoring Stations (PAMS) network in Taiwan.</p> <p>We evaluate model performance during a representative high-ozone event in fall 2021 and apply a top-down calibration approach using hourly VOC data from 12 PAMS sites. The original simulation (OrigSIM) significantly misrepresents key species, largely due to reliance on U.S.-based speciation profiles. After adjustment, the modified simulation (ModSIM) shows substantial improvements in both individual species concentrations and group-level composition (e.g., alkanes, aromatics). Notably, acetylene, a key tracer of incomplete combustion, was underestimated in OrigSIM but successfully recovered in ModSIM.</p> <p>Despite accounting for only ~32 % of total VOC emissions, PAMS species contribute up to 52 % of modeled domestic O₃ formation, highlighting their disproportionate impact in VOC-limited regimes. Additionally, the CMAQ-PAMS framework enables the use of diagnostic ratios (e.g., propylene/acetylene) to identify emission sources and assess air mass aging. These findings underscore the importance of localized VOC profiling and demonstrate that the PAMS-constrained CMAQ-PAMS model provides a more chemically detailed and observationally anchored platform for ozone modeling and regulatory applications.