Our previously developed method for the determination of three-ring and larger polynuclear aromatic hydrocarbons (P AH) of cigarette smoke was modified to allow quantitative determination of the more volatile P AH. Recovery tests with 14C-naphthalene showed that this smoke P AH was being lost to a large extent during the usual solvent evaporation steps. Special solvent removal techniques, using very efficient distillation equipment, were developed and tested to quantitatively recover the naphthalenes. The gas chromatographic profile for the volatile P AH, including naphthalenes, fluorenes, and related compounds, is discussed in relation to the modified procedure. Quantitative values for some of the PAH of cigarette smoke are given. The developed solvent removal and concentration techniques should be most applicable to the analysis of environmental samples containing volatile compounds.