Long-term air monitoring datasets are needed for persistent organic pollutants (POPs) to assess the effectiveness of source abatement measures and the factors controlling ambient levels. The Toxic Organic Micro Pollutants (TOMPs) Network, which has operated since 1991, collects ambient air samples at six sites across England and Scotland, using high-volume active air samplers. The network provides long-term ambient air trend data for a range of POPs at both urban and rural locations. Data from the network provides the UK Government, regulators and researchers with valuable information on emission/source controls and on the effectiveness of international chemicals regulation such as the Stockholm Convention and UN/ECE Protocol on POPs. The target chemicals of TOMPs have been polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and, since 2010, polybrominated diphenyl ethers (PBDEs). The continuous monitoring of these compounds demonstrates the constant decline in UK air concentrations over the last two decades, with average clearance rates for PCDD/Fs in urban locations of 5.1 years and for PCBs across all sites 6.6 years. No significant declines in rural locations for PCDD/Fs have been observed. There is a strong observable link between the declining ambient air concentrations and the emission reductions estimated in the annually produced National Atmospheric Emission Inventory (NAEI) dataset. These findings clearly demonstrate the unique strengths of long-term consistent datasets for the evaluation of the success of chemical regulation and control.