Brazilian petroleum is known by its high acidity due to the presence of acidic constituents, especially naphthenic acids (NA). The total characterization of the NA in petrochemical samples has been receiving special attention in research and comprises an analytical challenge, mainly due to the complexity of their mixtures. Gas chromatography with mass detector (GC/MS) is the technique of analysis more used, but recently comprehensive two-dimensional gas chromatography (GC × GC) has been used, due to its high resolution, peak capacity and sensitivity. The goal of this article is to discuss the techniques for sample preparation and analysis of NA in petroleum