A gas chromatography method, coupled with diode-array photometric spectral detection in the ultraviolet region (170-330 nm), was developed for the analysis of the gas phase of cigarette smoke. Several column configurations and elution profiles were employed in an effort to optimize peak resolution and compound identification efficiency. The final optimized method enabled us both to identify and quantify, the presence and the concentration of at least 15 volatiles in the gas phase stream of cigarette smoke. In that way, all major volatile organic compounds (including aldehydes, conjugated diens, ketones, furans and single ring aromatics), as well as nitric oxide, were analyzed in a straightforward manner through a single chromatographic run, of less than 50 min duration. The method can easily be implemented, by the introduction into the GC injection loop of a small volume from the gas phase steam, directly through the smoking apparatus exhaust circuit, thus providing an excellent alternative to existing available methods, that usually require several extraction steps prior to any chromatographic analysis. Furthermore, all problems concerning ageing of the gas phase are alleviated. The method was additionally proved very reliable as far as accuracy and reproducibility of the results is concerned. Finally, the proposed methodology was implemented through various experimental sets, in order to determine the relative abundance of the various cigarette smoke gas phase constituents in individual puffs as well as in different smoking regimes.