In order to characterize the main stream smoke while preserving its chemical compositions, two different approaches were developed. The first method is based on the trapping of the whole smoke at -183°C followed by the quantification of several smoke components using selected analytical techniques. The trapping is performed with a cryogenic instrument enabling a precise control of the temperature down to values as low as -190°C. After the trapping, the condensed smoke is diluted with a solvent and selected smoke components can be quantified using gas chromatography-mass spectrometry and liquid chromatography. The results obtained when trapping the main stream smoke of the 2R4F reference cigarette at -183°C were compared with those obtained by the standard methods. A good agreement was observed between the two approaches for 17 analytes, including some aldehydes, olefins, aromatic compounds and poly-aromatic compounds. The second method was designed to analyze the chemical composition of a single puff using gas chromatography-mass spectrometry. The smoke is sampled with a gas syringe, while the puff is being drawn. In order to evaluate the maximum number of puffs during one smoking run, an ultra-fast gas chromatograph-time of flight-mass spectrometer was used to analyze the smoke composition. The ultra-fast module enabled to analyze VOCs from isoprene to diterpenes in 1 minute. The evolution of the puff composition in the course of a smoking run was studied for the 2R4F reference cigarette, on components of both the gas and the particulate phases.