An LC/MS/MS method is presented for the determination of hydrogen cyanide in cigarette mainstream smoke. Cyanide is derivatized with 2,3'-naphthalenedicarboxaldehyde and taurine to form a benzo[f]isoindole derivative, which is then analyzed by LC/MS/MS. Isotopic KCN (K13C15N) was used as an internal standard. The regression equation was linear within the range 2.4-331 ng/mL for cyanide with a correlation coefficient > 0.999. The LOD was calculated as 4.1 ng/cigarette. The influence of the sodium hydroxide trapping solution concentration on the results is discussed. A 1 M solution showed the best results in terms of sample stability and trapping efficiency. The method proved to be robust, reliable, and more selective than current methods, making it a logical choice for determination of total cyanide in cigarette smoke.