Abstract: Currently, countries around the world are increasingly focused on managing harmful volatile organic compounds (VOCs) in ambient air. Data on harmful VOCs are becoming crucial for atmospheric environmental monitoring and control, significantly increasing in importance. The lists and information on harmful VOCs in the standards, regulations, and policy documents issued by various countries are scattered, and there is no centralized search channel or document that fully covers the VOCs data published by different countries. This makes it difficult to comprehensively and effectively utilize harmful VOCs data and information. Based on the chemical characteristics of harmful VOCs compounds, atmospheric environment monitoring and control, and the requirements for digital calibration certification and recognition of standard reference data, this article designs a technical route for establishing a dataset of harmful VOCs compounds and its establishment methods. The establishment process is completed in practice. The harmful VOCs reference dataset has become a standard dataset after self-assessment, data inspection, comparison between Chinese and American datasets, and expert review. This dataset is publicly available on the official website of the National Metrology Science Data Center, providing important data resources such as authoritative maps of harmful VOCs for scientific research and the development of the environmental protection industry. It greatly enhances scientific research autonomy and has reference value for the governance and research of harmful VOCs. It also lays the foundation for subsequent digital calibration certification and recognition.