Volatile organic compounds (VOCs) are the dominant pollutants in industrial parks. However, they are not generally considered as part of the air quality index (AQI) system, which leads to a biased assessment of pollution in industrial parks. In this study, a supplementary assessment system of AQI-V was established by analyzing VOCs characteristics with vehicle-mounted PTR-TOFMS instrument, correlation analysis and the standards analysis. Three hourly and daily scenarios were considered, and the hierarchical parameter setting was further optimized by field application. The hourly and daily assessments revealed the evaluation factors for the discriminability of different air quality levels, practiced value for regional air quality improvement, and the reservation of general dominant pollutants. Finally, the universality testing in ZPIP successfully recognized most of the peaks, with 54.76%, 38.39% and 6.85% for O3, VOCs and NO2 as the dominant pollutant, and reflected the daily ambient air quality condition, together with the dominant pollutant. The AQI-V system with VOCs sub-index is essential for air quality evaluation in industrial parks, which can further provide scientific support to control the pollution of VOCs and the secondary pollutant, therefore significantly improve the air quality in local industrial parks.