Comprehensive two-dimensional gas chromatography (GC x GC) was applied to the study of cachaca production. Effects of bidistillation, and the use of charcoal filtration in the production of artisan cachaca, as well as the effects of mlulti-distillation on volatile products in commercial cachaca were investigated. Volatile compounds were collected and concentrated onto a polyacrylate solid-phase microextraction fibre, and analyzed using GC x GC on a non-polar (BPX5)-polar (BP20) column set. More than 100 compounds, comprising various homologous series were tentatively identified using MS library matching and comparison with retention indices. Phthalate organic contamination following the use of ion exchange resin for removal of copper ion was evident. Charcoal successfully removes this contamination product. Prediction Of Compounds within particular homologous series aids component identification.