Cachaça may be contaminated by a remarkable presence of polycyclic aromatic hydrocarbons (PAHs) when the sugar cane crop used for its production is burned before harvesting. The analysis of 15 PAHs by liquid chromatography coupled to a fluorescence detector in 131 cachaça samples from burned and nonburned sugar cane crops is reported. Average contents of 21.1 and 1.91 microg L(-1) for total PAHs were observed for cachaças originating from burned and nonburned sugar cane plantations, respectively. The main difference between these two classes of cachaças is in the quantitative profile of the most potent carcinogenic PAH, benzo[a]pyrene, which is more abundant in cachaça produced from burned sugar cane crops (4.54 x 10(-2) microg L(-1)) than in cachaça produced from nonburned crops (9.02 x 10(-3) microg L(-1)). The contents of benzo[a]pyrene in both classes of cachaça are lower than the legal limit established by the European Union (EU) at 2.00 microg L(-1) for food products. In relation to the total PAH content suggested by the German Society for Fat Science, both cachaças from burned (21.1 microg L(-1)) and nonburned crops (1.91 microg L(-1)) are below the limit (25 microg L(-1)) for total PAH content. The analytical data for PAHs, when treated through the multivariate statistical methods principal component analysis and canonical discriminant analysis, provide a very good distinction between samples produced from burned and nonburned sugar cane crops with a certainty of 98.1%.