There is a growing demand for rapid analytical systems to detect the presence of humans who are either entrapped as a result of a disaster or, in particular, hidden, as in the case of smuggling or trafficking. The trafficking and smuggling of people to Europe have reached epidemic proportions in recent years. This does not only put a major strain on European resources, but puts at risk the health and lives of the people being trafficked or smuggled. In this context, the early detection and interception of smuggled/trafficked people is of particular importance in terms of saving migrants from life-threatening situations. Similarly, the early and rapid location of entrapped people is crucial for urban search and rescue (USaR) operations organized after natural or man-made disasters. Since the duration of entrapment determines the survivability of victims, each novel detecting tool could considerably improve the effectiveness of the rescue operations and hence potentially save lives. Chemical analysis aiming at using a volatile chemical fingerprint typical for the presence of hidden humans has a huge potential to become an extremely powerful technology in this context. Interestingly, until now this approach has received little attention, despite the fact that trained dogs have been used for decades to detect the presence of buried people through scent. In this article we review the current status of using analytical techniques for chemical analysis for search and rescue operations, and discuss the challenges and future directions. As a practical implementation of this idea, we describe a prototype portable device for use in the rapid location of hidden or entrapped people that employs ion mobility spectrometry and a sensor array for the recognition of the chemical signature of the presence of humans.