Analysis of plant volatile organic compounds (VOCs) and essential oils (EOs, collectively called the plant volatilome) is an invaluable technique in plant biology, as it provides the qualitative and quantitative composition of bioactive compounds. From a physiological standpoint, the plant volatilome is involved in some critical processes, namely plant-plant interactions, the signaling between symbiotic organisms, the attraction of pollinating insects, a range of biological activities in mammals, and as an endless source of novel drugs and drug leads. This chapter analyses and discusses the most advanced methods of analysis of the plant volatilome.