Recent advancements in person-portable instrumentation have resulted in the potential to provide contemporaneous results through rapid in-field analyses. These technologies can be utilised in emergency response scenarios to aid first responders in appropriate site risk assessment and management. Large metropolitan fires can pose great risk to human and environmental health due to the rapid release of hazardous compounds into the atmos-phere. Understanding the release of these hazardous organics is critical in understanding their associated risks. Person-portable gas chromatography-mass spectrometry (GC-MS) was evaluated for its potential to provide rapid on-site analysis for real-time monitoring of hazardous organic compounds at fire scenes. Air sampling and analysis methods were devel-oped for scenes of this nature. Controlled field testing demonstrated that the portable GC-MS was able to provide preliminary analytical results on the volatile organic compounds present in air samples collected from both active and extinguished fires. In-field results were confirmed using conventional laboratory-based air sampling and analysis procedures. The deployment of portable instrumentation could provide first responders with a rapid on-site assessment tool for the appropriate management of scenes, thereby ensuring environmental and human health is proactively protected and scientifically informed decisions are made for the provision of timely advice to stakeholders.