Solid phase microextraction (SPME) is a simple, cost-effective, time-saving extraction technique. It is rapid and highly sensitive. In this study, organic acids in cigarette smoke were extracted with 85 microns polyacrylate coated fiber. Volatile and semi-volatile organic acids, such as butanoic acid, hexanoic acid, 2-furancarboxylic acid, octanoic acid, nonanoic acid, benzoic acid, phenylacetic acid, tetradecanoic acid, and hexadecanoic acid from cigarette smoke were converted to their esters by using methanolic derivatization agent. The esters were extracted by using headspace solid phase microextraction and determined quantitatively by gas chromatography with selected ion monitoring mode mass spectrometry. Qualitative analysis of 4 brands cigarette smoke demonstrated the usefulness of this analytical technique of volatile and semi-volatile acids in cigarette smoke. More than sixty organic acids were detected by using this method.