The composition of smoke emanating from a burning cigarette is influenced _ beside others _ by the coal temperature, but very little is known about the evolution of the smoke composition during a single puff and its link to the actual coal temperature. Therefore, the objective of this study was to investigate simultaneously the temperature distribution within the cigarette coal and the chemical composition of the smoke (constituents like nicotine, degradation products from cellulose, sugars, or from tobacco waxes). The experiment was done with a single port smoking machine. The chemical analysis has been performed by means of gas chromatography. The GC was coupled to the smoking machine by a sliding valve technique, which allowed to inject a small part of a single puff without any modification of the flow profile in the cigarette. A standard infrared video system was used to measure the coal temperature distribution. The video technique allowed together with the trigger signal from the valve an exact correlation of the two measurements. A statistical evaluation of the amounts of smoke constituents, identified by the GC-system, in relation to their estimated production temperatures, resulted in most probable temperature ranges for the different substances.