Exposure to persistent organic pollutants (POPs) and related compounds such as PCBs, brominated flame retardants, organochlorine pesticides and PAHs is regarded as an important environmental risk factor for humans. Recently concerns about POPs resulted in the international protocol called the Stockholm Convention on POPs. Air quality standards (indoor, outdoor and occupational) for PAHs and other POPs will also be applied in the EU in the future. This will bring requirements for monitoring, to check for compliance and to reduce human exposures to POPs. This can occur from point sources and in various microenvironments, indoors, outdoors and in workplaces. Monitoring can be undertaken either by an active (pumped) method or using a passive (diffusive) air sampling (PAS) device. To date, PAS for POPs have mainly been used as integrating (long-term) samplers for ambient (outdoor) air. However, there are several reasons to develop PAS for monitoring of POPs in occupational and indoor environments. We discuss the potential advantages, limitations and developments needed, so that PAS can be used reliably and routinely indoors and in occupational settings for POPs.