The impact of bioaerosol emissions from urban, agricultural and industrial environments on local air quality is of growing policy concern. Yet the risk exposure from outdoor emissions is difficult to quantify in real-time as microbial concentration in air is low and varies depending on meteorological factors and land use types. While there is also a large number of sampling methods in use, there is yet no standardised protocol established. In this review, a critical insight into chemical fingerprint analysis of microbial volatile organic compounds (MVOC) is provided. The most suitable techniques for sampling and analysing MVOCs in outdoor environments are reviewed and the need for further studies on MVOCs from outdoor environments including background levels is highlighted. There is yet no rapid and portable technique that allows rapid detection and analysis of MVOCs on site. Further directions towards a portable GC–MS coupled with SPME or an electronic nose are discussed.