Measurement of water in petroleum and petroleum-based products is of industrial and economic importance; however, the varied and complex matrixes make the analyses difficult. These samples tend to have low amounts of water and contain many compounds which react with iodine, causing Karl Fischer titration (KFT) to give inaccurate, typically higher, results. A simple, rapid, automated headspace gas chromatography (HSGC) method which requires modified instrumentation and ionic liquid stationary phases was developed. Measurement of water in 12 petroleum products along with 3 National Institute of Standards and Technology reference materials was performed with the developed method. The range of water found in these samples was ∼12–3300 ppm. This approach appeared to be unaffected by complicated matrixes. The solvent-free nature of the HSGC method also negates the solubility limitations which are common with KFT.