The monitoring of volatile organic compounds (VOCs) from industrial and ambient sources plays a critical role in air quality management, contributing data for legislative requirements. Emitted from sources such as biomass burning and power stations, VOCs contribute to ozone formation, which impacts environmental visibility, and promotes smog, acid rain, and ozone depletion. Various sampling and analysis methods are employed to monitor VOCs, relying on quality protocols to ensure data reliability. Calibration of VOC measurement equipment involves gas reference standards linked to the international system of units (SI) through primary methods like gravimetry. The objective is to elaborate the impact of these reference gas mixtures in the monitoring of VOC. This chapter focuses on the role of VOC reference gas mixtures in monitoring, emphasizing manufacturing methods, data comparability from proficiency testing schemes, and global data consistency. The key findings in this chapter highlight the real-time data analytics, machine learning algorithms for predictive modelling, and dispersion of sensor networks as the potential advancements in VOCs monitoring to improve capacity to identify and address new pollution patterns that will have significant impact on the improved public health protection and air quality management.