Volatile organic compounds in air, especially the reactive biogenic hydrocarbons (e.g., isoprene and monoterpenes), play important roles in the chemistry of the troposphere even at very low concentrations. Sensitive and reliable detection methods are required in order to determine their low concentrations in air and to estimate their emission fluxes from sources. The flame ionization detector and the mass spectrometer have been widely used for the quantitative and qualitative analysis of biogenic non-methane hydrocarbons in air but other detection systems are available. Both the sampling and analytical methods used for these measurements are summarized in this review. The possible applications of several potential detection methods and recent developments in the use of new methods are also discussed.